Method for pretreating and/or coating metallic surfaces with a paint-like coating prior to forming and use of substrates coated in this way

ABSTRACT

The invention relates to a method for coating a metallic strip. The strip or optionally, the strip sections produced from said strip in the subsequent process, is/are first coated with at least one anticorrosion layer—according to an alternative form of embodiment, this can be left out—and then with at least one layer of a paint-like coating containing polymers. After being coated with at least one anticorrosion layer or after being coated with at least one layer of a paint-like coating, the strip is divided into strip sections. The coated strip sections are then formed, joined and/or coated with at least one (other) paint-like coating and/or paint coating. The paint-like coating is formed by coating the surface with an aqueous dispersion containing the following in addition to water: a) at least one organic film former containing at least one water-soluble or water-dispersed polymer with an acid value of 5 to 200; b) at least one inorganic compound in particle form with an average particle diameter measured on a scanning electron microscope of 0.005 to 0.3 μm; and c) at least one lubricant and/or at least one corrosion inhibitor. The metallic surface that is optionally coated with at least one anticorrosion layer is brought into contact with the aqueous composition and a film containing particles is formed on the metallic surface, this film then being dried and optionally also hardened, the dried and optionally, also hardened film having a layer thickness of 0.01 to 10 μm. The invention also relates to a corresponding aqueous composition.

[0001] The invention relates to a method of coating metallic surfacesand also to the use of the coated substrates produced by the method ofthe invention in particular in vehicle construction, especially in theline manufacture of automobiles, and for the production of components orbodywork parts or premounted elements in the vehicle, air travel orspace travel industry. It relates in particular to new possibilities forthe preparation and assembly of motor vehicles which no longer involvethe current standard practice of assembling the various parts of thebody, cleaning and phosphating them and only then painting them with thepaint system as a whole.

[0002] There is a need for even greater rationalization of themanufacture of vehicle bodies and their individual parts and also ofpaneling for vehicles and aircraft.

[0003] The anticorrosion layer(s) ought to be readily formable togetherwith the paint or a paintlike layer and ought also to exhibit, afterforming, effective corrosion protection and effective paint adhesion.Additionally, depending on the joining technique, it may be necessaryfor said layer(s) to be readily clinchable as well without showing agreater tendency toward corrosion as a result.

[0004] For producing paint-coated metal sheets there are already methodssimilar to the production methods for metal sheets precoated on thestrip, which are used for household appliances, metal architecturalpanels, and furniture. The requirements imposed on these sheets,however, are much less stringent than the requirements in particular inautomobile engineering and aircraft construction. This is because therequirements in the vehicle, air travel or space industry in terms ofthe strength of the coated sheets, the joining technologies, the paintsystem, and the properties of the paint layers, such as brightness,gloss, corrosion resistance, scratch resistance, paint adhesion, andstonechip resistance, are markedly different and influence the complexmanufacturing process. The high-grade properties of these sheets muststill be sufficiently high in the region of the formed and joinedportions in particular. Normally, the same exacting requirements asthose imposed at present are imposed on a different manufacturingprocess and a different layer structure, even when individual layers arethinner than 4 μm. The composition of the coating used for this purpose,comprising polymers and particles, is also novel, to the knowledge ofthe applicant.

[0005] The basecoat for metal architectural panels on the outsidepresently often contains chromate, in order to provide increasedcorrosion resistance at a relatively low layer thickness; applied to thebasecoat there is normally a topcoat with a thickness in the range from10 to 20 μm. The same or similar basecoats as on the facing side areoften applied to the inside of metal architectural panels, as areverse-face coating, with a thickness in the range from 6 to 15 μm, asa single paint layer. To date, however, to the knowledge of theapplicant, there has been no use of UV-cured paint materials in thecoating of strips in the household appliance and architectural segments.

[0006] The strip line which is utilized in each case may be agalvanizing line, a coil coating line and/or another kind of coatingline, such as, for example, a painting line in, for example, anautomobile plant, on which cut strip which has been pretreatedbeforehand on a strip line is painted with a paint and/or with apaintlike coating.

[0007] By prephosphating is meant a temporary protection of metallicsurfaces, it being possible for the substrates thus coated to besubsequently subjected, where appropriate, to oiling, temporary storage,forming, joining (after deoiling) by clinching, adhesive bonding and/orwelding, for example, and/or pretreated again with phosphate, forexample, before the paint system is applied.

[0008] Pretreatment prior to painting is nowadays carried out,particularly in the European automobile industry, sometimes withoutdeliberate addition of chromium and sometimes with addition of chromium.In principle, however, it is preferred to operate without chromium orsubstantially without chromium, in particular without chromium to theextent that no chromium is deliberately added, in order to avoid thistoxic heavy metal. Nevertheless, the addition of chromium has aparticular corrosion protection effect, given that a self-healing effectmay come about at a site which has been damaged. The pretreatmentsolutions are preferably also free from or contain low levels in eachcase of cobalt, copper, nickel and/or other heavy metals. Amounts ofnickel in particular, however, are still particularly advantageous andare therefore virtually always present in phosphate coats, for example.The pretreatment solutions can be applied either by the rinse method orby the no-rinse method. In the case of the rinse method, the applicationof the solution, which can take place in particular by spraying and/ordipping and during which the pretreatment layer is formed, is followedby rinsing. In the case of the no-rinse method, the solution is appliedwith a roll coater, for example, and is dried immediately withoutrinsing.

[0009] By a basecoat is meant a paint or a paintlike coating whichreplaces the cathodic dip coat (electrocoat) that is commonly used inbodywork construction. It may be a primer, in particular a lubricantprimer, welding primer or pretreatment primer, or another kind ofcoating, based for example on silane/siloxane. When necessary, anintermediate paint layer may be applied between the basecoat and thesurfacer (i.e., color coating). The surfacer is normally followed by atleast one clearcoat, which intensifies the brightness and is alsoreferred to as the topcoat.

[0010] The coating which is developed with a lubricant primer can beformed very effectively and easily owing to the good slip properties,its low friction, and its flexibility. A welding primer and the coatingproduced from it includes such a high fraction of electricallyconductive substance, in particular of electrically conductiveparticles, that two metal sheets can be welded together withoutsubstantially increased effort even when this involves contactingthrough two paintlike coats. A pretreatment primer is a primer or acorresponding coating which may also replace the corrosion protectionproperties of a pretreatment layer. All of these are paintlike coatings.

[0011] The invention further relates to a method of coating metallicsurfaces with an aqueous composition comprising polymer and fineinorganic particles. The invention additionally relates to such anaqueous composition and also to the use of the substrates coated by themethod of the invention.

[0012] The processes used most frequently to date for the surfacetreatment or pretreatment prior to painting of metals, particularly ofmetal strip, are based on the use of chromium(VI) compounds togetherwith diverse additives. Owing to the toxicological and environmentalrisks which such processes entail and, moreover, owing to theforeseeable statutory restrictions on the use of chromate-containingprocesses, the search has been on for some time already for alternativesto these processes in all fields of metal surface treatment.

[0013] Resin mixtures are known for which resins are blended withinorganic acids in order thus to obtain a pickling attack as well andhence a better contact of the resin coat directly with the metallicsurface. These compositions have the drawback that, owing to thepickling attack, contamination occurs during the contacting of thetreatment liquid (dispersion) to the substrate. This leads to theaccumulation of metals in the treatment liquid and, as a result, to apermanent change in the chemical composition of the treatment liquid,thereby significantly impairing the corrosion protection. These metalsare dissolved by the pickling attack out of the metallic surface of thesubstrate to be treated.

[0014] Another drawback is that, especially in the case of aluminum andaluminum-containing alloys, the surfaces darken, discoloring in certaincircumstances to a dark gray to anthracite color. The darkened metalsurfaces cannot be used for decorative applications, since thediscoloration is undesirable on esthetic grounds alone. Depending on thethickness of the applied layer, the darkening is visible with varyingintensity.

[0015] The object was therefore to overcome the drawbacks of the priorart and in particular to propose a method of coating metallic surfaceswhich is also suitable for high coating speeds, such as are used forstrips; which can be employed substantially or entirely free fromchromium(VI) compounds; which as far as possible is also free fromorganic and inorganic acids; and which can be employed industrially.

[0016] It is an object of the invention to propose a method of coatingmetallic substrates which are also suitable for the coating of stripsrunning at speed and with which it is possible to apply organic,sufficiently flexible, and at the same time sufficientlycorrosion-resistant coatings, which allow the production of a basecoatand, where appropriate, of the subsequent layers as well. This methodought to be suitable for economic and very environmentally friendlyindustrial implementation.

[0017] A further object was to propose a method for producing parts, inparticular for the assembly of automobile bodies, with which it ispossible to perform a longer part of the manufacturing operation of theparts, where appropriate still in the form of a strip, than was hithertothe case in a strip line.

[0018] The object is achieved by a method of coating a metallic strip,the strip, or where appropriate strip sections produced from it, in thesubsequent operation, being first coated with at least one anticorrosionlayer and then with at least one layer of a paintlike,polymer-containing layer, the strip, after coating with at least oneanticorrosion layer or after coating with at least one layer of apaintlike coating, being divided into strip sections, the coated stripsections then being formed, joined and/or coated with at least one(further) paintlike layer and/or paint layer, the paintlike coatingbeing formed by coating the surface with an aqueous dispersion whichcomprises besides water a) at least one organic film former comprisingat least one water-soluble or water-dispersed polymer having an acidnumber in the range from 5 to 200, b) at least one inorganic compound inparticle form, having an average particle diameter, measured in ascanning electron microscope, in the range from 0.005 up to 0.3 μmdiameter, and c) at least one lubricant and/or at least one corrosioninhibitor, the metallic surface coated with at least one anticorrosionlayer being contacted with the aqueous composition and aparticle-containing film being formed on the metallic surface, andsubsequently dried and, as the case may be, additionally cured, thedried and, as the case may be, additionally cured film having athickness in the range from 0.01 to 10 μm.

[0019] The object is further achieved by a method of coating a metallicstrip, the strip being coated with at least one layer of a paintlike,polymer-containing coat without an anticorrosion layer being appliedbeforehand, the strip, after coating with at least one layer of apaintlike coating, being divided into strip sections, the coated stripsections then being formed, joined and/or coated with at least one(further) paintlike layer and/or paint layer, the paintlike coatingbeing formed by coating the surface with an aqueous dispersion whichcomprises besides water a) at least one organic film former comprisingat least one water-soluble or water-dispersed polymer having an acidnumber in the range from 5 to 200, b) at least one inorganic compound inparticle form, having an average particle diameter, measured in ascanning electron microscope, in the range from 0.005 up to 0.3 μmdiameter, and c) at least one lubricant and/or at least one corrosioninhibitor, the clean metallic surface being contacted with the aqueouscomposition and a particle-containing film being formed on the metallicsurface, and subsequently dried and, as the case may be, additionallycured, the dried and, as the case may be, additionally cured film havinga thickness in the range from 0.01 to 10 μm.

[0020] The surfaces coated in these methods are metallic surfaces inparticular of aluminum, iron, copper, magnesium, nickel, titanium, tin,zinc or alloys of aluminum, iron, copper, magnesium, nickel, titanium,tin and/or zinc. The aqueous composition used may in this case besubstantially or entirely free from chromium(VI) compounds. It may servefor pretreatment prior to a further coating, such as painting, forexample, or for the treatment wherein the element to be coated, whereappropriate—in particular a strip or strip section—is formed aftercoating. In particular, however, the intention is that it should serveto form a first and/or second paintlike coating.

[0021] In addition to the abovementioned constituents it may comprisewhere appropriate at least one organic solvent, where appropriate atleast one silane and/or siloxane calculated as silane, where appropriateat least one crosslinking agent based in particular on a basic compound,and where appropriate at least one chromium(VI) compound.

[0022] The thickness of the dried and, where appropriate, also curedfilm can be determined by detaching a defined area of the film andweighing it.

[0023] The dried and, where appropriate, also cured film preferably hasa pendulum hardness of from 30 to 190 s, preferably from 50 to 180 s,measured with a König pendulum hardness tester in accordance with DIN53157. The König pendulum hardness is situated preferably in the rangefrom 60 to 150 s, more preferably in the range from 80 to 120 s. In thecase of UV-crosslinkable coatings figures in the range of from 100 to150 s often appear for the pendulum hardness, while in the case of thenon-UV-crosslinkable coatings or coatings based on polymer dispersionswhich undergo little or no chemical crosslinking, for example, it ispossible preferentially for pendulum hardness figures in the range from40 to 80 s to appear. The layers produced in accordance with theinvention are to be tested only on test specimens having chemicallyuniform but sufficiently thick layers, but not on thin coatings in therange up to 10 μm in thickness.

[0024] The dried and, where appropriate, also cured film preferably hasa flexibility such that bending over a conical mandrel in a mandrelbending test very substantially in accordance with the DIN ISO 6860 fora mandrel of from 3.2 mm to 38 mm in diameter, but without scoring ofthe test area, does not produce any cracks longer than 2 mm which areperceptible on subsequent wetting with copper sulfate as a result ofcolor change due to deposition of copper on the cracked metallicsurface. Demonstration of the flexibility by using the mandrel bendingtest and subsequently immersing the regions subjected to forming in thisway in a copper sulfate solution to visualize defects ensures areproducible test result and has the advantage that it does notnecessitate any laborious corrosion tests, lasting for example for 240hours, which in some cases, depending on chemical composition androughness of the metallic surface, can lead to different results whichare therefore of only limited comparability with one another. In thecase of relatively base-metallic surfaces such as in the case ofaluminum alloys it is necessary for this test first to clean themetallic surface by pickling prior to coating in order verysubstantially to remove the oxide layer.

[0025] Inventive Composition for Developing a Treatment Layer orPretreatment Layer and/or a Paintlike Coating:

[0026] The aqueous composition is preferably free from inorganic acidsand/or from organic carboxylic acids, especially free from inorganicacids.

[0027] The organic film former is present in the aqueous composition(bath solution) preferably in an amount of from 0.1 to 1000 g/L, morepreferably in a range from 2 to 600 g/L, very preferably from 50 to 550g/L, in particular from 150 to 450 g/L. It is preferred to add from 2 to100 parts of the organic film former per 100 parts by weight of water,more preferably from 10 to 60 parts, very preferably from 15 to 45parts. The highest levels of organic film former may occur in particularin the case of UV-curing systems with few or no volatile fractions suchas organic solvents and/or residual monomers. Particularly preferred forthe method of the invention are coatings which film predominantly orsolely on drying, or thermally-physically cured coatings.

[0028] The at least one inorganic compound in particle form is presentin the aqueous composition (bath solution) preferably in an amount offrom 0.1 to 500 g/L, more preferably in a range from 10 to 200 g/L, verypreferably from 30 to 100 g/L. It is preferred to add from 0.1 to 50parts of the at least one inorganic compound in particle form per 100parts by weight of water, more preferably from 0.5 to 20 parts, verypreferably from 0.8 to 10 parts. Among the inorganic compounds inparticle form particular preference is given to those which maintain thetransparency of the coating of the invention, i.e. which are colorlessor white, such as alumina, barium sulfate, silicate, silica, colloidalsilica, zinc oxide and/or zirconium oxide, for example, in order to keepthe visual character of the metallic surface visible as far as possiblewithout corruption.

[0029] The ratio of the amounts of organic film former to amount ofinorganic compounds in particle form in the aqueous composition (bathsolution) can vary within wide ranges; in particular, it can be 2 25:1.This ratio is preferably situated within a range from 0.05:1 to 15:1,more preferably within a range from 1:1 to 8:1.

[0030] The amount of at least one silane and/or siloxane calculated assilane in the aqueous composition (bath solution) is preferably from 0.1to 50 g/L, more preferably from 0.2 to 35 g/L, very preferably from 0.5to 20 g/L, in particular from 1 to 10 g/L.

[0031] For a concentrate for making up the bath solution primarily bydilution with water, or for a top-up solution for standardizing the bathsolution when a bath is operated for prolonged periods, it is preferredto use aqueous compositions which contains the majority or almost all ofthe constituents of the bath solution, but not the at least oneinorganic compound in particle form, which is preferably held separateand added separately. In addition, reaction accelerants and dryingaccelerants such as, for example, the morpholine salt ofparatoluenesulfonic acid can be added separately, especially for curingin the case of polyester-melamine resin systems. The concentrate and thetop-up solution, respectively, preferably have a concentration which interms of the individual constituents is from five times to ten times thelevels in the bath solution. In some cases, however, it is also possibleto operate with the “concentrate” directly as bath solution, whereappropriate after slight dilution by from 5 to 30%, for example.

[0032] The aqueous composition, which is preferably substantially freeof chromium(VI) compounds, has a chromium content of only up to 0.05% byweight on chromium-free metallic surfaces and only up to 0.2% by weighton chromium-containing metallic surfaces. Preferably, no chromium isadded deliberately to the solution or dispersion. Amounts of chromiumoccurring in the bath can then have been dissolved out of the metallicsurface by pickling attack, can originate or have been entrained intraces from contaminants, from upstream baths, and/or can come fromvessels and pipelines. Preferably, amounts of cadmium, nickel, cobaltand/or copper are also kept extremely low, and are not added. Normally,however, for the solutions and dispersions of the invention, thepickling attack is so slight that it is not possible for any steeladditives such as chromium or nickel, for example, to be dissolved outof a steel surface.

[0033] In the case of the method of the invention the organic filmformer can be present in the form of a solution, dispersion, emulsion,microemulsion and/or suspension. The term “dispersion” here encompassesthe subsidiary concepts of emulsion, microemulsion, and suspension. Theorganic film former may be or comprise at least one synthetic resin,especially a synthetic resin based on acrylate, butadiene, ethylene,polyester, polyurethane, silicone polyester, epoxide, phenol, styrene,urea-formaldehyde, mixtures thereof and/or addition copolymers thereof.The system in question may be a cationically, anionically and/orsterically stabilized synthetic resin or polymer and/or solutionthereof.

[0034] The organic film former is preferably a synthetic resin mixtureand/or an addition copolymer which includes synthetic resin based onacrylate, epoxide, ethylene, urea-formaldehyde, phenol, polyester,polyurethane, styrene and/or styrene-butadiene, and from which, duringor after the emission of water and other volatile constituents, anorganic film is formed. The organic film former may comprise syntheticresin and/or polymer based on epoxide, phenol, polyacrylate,polyethyleneimine, polyurethane, polyvinyl alcohol, polyvinylphenol,polyvinylpyrrolidone, polyaspartic acid and/or derivatives thereofand/or copolymers, particularly copolymers with a phosphorus-containingvinyl compound.

[0035] Very particular preference is given to a synthetic resin based onacrylate or based on ethylene-acrylic acid with a melting point in therange from 60 to 95° C. or to a synthetic resin having a melting pointin the range from 20 to 160° C., in particular in the range from 60 to120° C.

[0036] The acid number of the synthetic resin/synthetic resin mixturemay lie preferably in the range from 10 to 140, more preferably in therange from 15 to 100, very preferably in the range from 20 to 80. Withina high acid number range it is normally not necessary to stabilize afilm former cationically, anionically and/or sterically. In the case ofa low acid number, however, such stabilization is generally necessary.In that case it is advantageous to use synthetic resins which havealready been stabilized, or mixtures thereof.

[0037] The molecular weight of the synthetic resin or the polymer maylie within the range from at least 1000 u, preferably from 5000 to 250000 u, more preferably in the range from 20 000 to 200 000 u.

[0038] In the case of the method of the invention, the pH of the aqueoussolution of the organic film former without the addition of furthercompounds may lie preferably in the range from 0.5 to 12, morepreferably in the range from 1 to 6 or from 6 to 10.5, very preferablyin the range from 1.5 to 4 or from 7 to 9, depending on whether themethod is carried out in the acidic or rather the basic range. In thiscontext it should be borne in mind that the synthetic resins have oftenalready been neutralized at the premises of the synthetic resinmanufacturer. Preferably, the pH of the organic film former alone in anaqueous formulation, without addition of further compounds, is in therange from 1 to 12. If, however, the pH should have dropped as a resultof storage of the synthetic resins or of the mixtures, it can be usefulto return the pH, in particular of the otherwise ready-to-usesolution/dispersion, to a more alkaline range by means, for example, ofadding sodium hydroxide solution.

[0039] The composition of the organic film former may also be such thatit contains (only) water-soluble synthetic resin and/or polymer,especially resin and/or polymer stable in solutions with pH values ≦5.

[0040] The organic film former preferably contains (only) syntheticresin and/or polymer containing carboxyl groups. The carboxyl groups canbe neutralized, inter alia, by ammonia, amines—especiallyalkanolamines—and/or alkali metal compounds and can be reacted to givean aqueous solution with a readily water-dilutable synthetic resin,which beforehand under standard conditions is not soluble in water. Forcrosslinking the carboxyl-containing synthetic resins it is advantageousto add melamine-formaldehyde for chemical crosslinking.

[0041] In the case of the method of the invention it can be preferablefor the aqueous composition to comprise at least one partly hydrolyzedor fully hydrolyzed silane and/or at least one siloxane. This thenoffers the advantage that adhesion bridges are produced between thesubstrate and the dried protective film and also to plastics coatingsand/or paint layers possibly applied subsequently, so also achievingimproved paint adhesion. A further advantage is that appropriatesilanes/siloxanes produce adhesion-bridgelike cross-links within thedried protective film which substantially enhance the strength and/orflexibility of the coating system and also the adhesion to thesubstrate, thereby achieving improved adhesion in the case of many paintsystems. In the case of the method of the invention it can be preferablefor the aqueous composition to comprise at least one partly hydrolyzedor fully hydrolyzed silane. This then offers the advantage that, in thecase of many paint systems, improved adhesion is obtained. The silanemay be an acyloxysilane, an alkylsilane, an alkyltrialkoxysilane, anaminosilane, an aminoalkylsilane, an aminopropyltri-alkoxysilane, abis-silyl-silane, an epoxysilane, a fluoroalkylsilane, aglycidyloxysilane such as, for example, aglycidyloxyalkyltrialkoxysilane, an isocyanatosilane, a mercaptosilane,a (meth)acrylato-silane, a mono-silyl-silane, a multi-silyl-silane, abis(trialkoxysilylproyl)amine, a bis(trialkoxysilyl)-ethane, asulfur-containing silane, a bis(trialkoxy-silyl)propyltetrasulfane, aureidosilane such as, for example, a (ureidopropyltrialkoxy)silaneand/or a vinylsilane, in particular a vinyltrialkoxysilane and/or avinyltriacetoxysilane. It can be, for example, at least one silane in amixture with an amount of at least one alcohol such as ethanol, methanoland/or propanol of up to 8% by weight based on the silane content,preferably up to 5% by weight, more preferably up to 1% by weight, verypreferably up to 0.5% by weight, where appropriate with an amount ofinorganic particles, in particular in a mixture of at least oneaminosilane such as, for example, bis-amino-silane with at least onealkoxysilane such as, for example, trialkoxysilylpropyltetrasulfane or avinylsilane and a bis-silyl-aminosilane or a bis-silyl-polysulfursilaneand/or a bis-silyl-aminosilane or an aminosilane and amulti-silyl-functional silane. The aqueous composition can in that casealso, alternatively or additionally, contain at least one siloxanecorresponding to the abovementioned silanes. Preference is given tothose silanes/siloxanes which have a chain length in the range from 2 to5 carbon atoms and contain a functional group which is suitable forreaction with polymers. The addition of at least one silane and/orsiloxane may be advantageous for the purpose of developing adhesionbridges or for promoting crosslinking.

[0042] In the case of the method of the invention the inorganic compoundin particle form that is added is a finely divided powder, a dispersionor a suspension, such as, for example, a carbonate, an oxide, a silicateor a sulfate, especially colloidal and/or amorphous particles. Withparticular preference the inorganic compound in particle form comprisesparticles based on example, a glycidyloxyalkyltrialkoxysilane, anisocyanatosilane, a mercaptosilane, a (meth)acrylato-silane, amono-silyl-silane, a multi-silyl-silane, abis(trialkoxysilylproyl)amine, a bis(trialkoxysilyl)-ethane, asulfur-containing silane, a bis(trialkoxy-silyl)propyltetrasulfane, aureidosilane such as, for example, a (ureidopropyltrialkoxy)silaneand/or a vinylsilane, in particular a vinyltrialkoxysilane and/or avinyltriacetoxysilane. It can be, for example, at least one silane in amixture with an amount of at least one alcohol such as ethanol, methanoland/or propanol of up to 8% by weight based on the silane content,preferably up to 5% by weight, more preferably up to 1% by weight, verypreferably up to 0.5% by weight, where appropriate with an amount ofinorganic particles, in particular in a mixture of at least oneaminosilane such as, for example, bis-amino-silane with at least onealkoxysilane such as, for example, trialkoxysilylpropyltetrasulfane or avinylsilane and a bis-silyl-aminosilane or a bis-silyl-polysulfursilaneand/or a bis-silyl-aminosilane or an aminosilane and amulti-silyl-functional silane. The aqueous composition can in that casealso, alternatively or additionally, contain at least one siloxanecorresponding to the abovementioned silanes. Preference is given tothose silanes/siloxanes which have a chain length in the range from 2 to5 carbon atoms and contain a functional group which is suitable forreaction with polymers. The addition of at least one silane and/orsiloxane may be advantageous for the purpose of developing adhesionbridges or for promoting crosslinking.

[0043] In the case of the method of the invention the inorganic compoundin particle form that is added is a finely divided powder, a dispersionor a suspension, such as, for example, a carbonate, an oxide, a silicateor a sulfate, especially colloidal and/or amorphous particles. Withparticular preference the inorganic compound in particle form comprisesparticles based on at least one compound of aluminum, of barium, ofcerium, of calcium, of lanthanum, of silicon, of titanium, of yttrium,of zinc and/or of zirconium, especially particles based on alumina,barium sulfate, cerium dioxide, silica, silicate, titanium oxide,yttrium oxide, zinc oxide and/or zirconium oxide. As organic compound inparticle form it is preferred to use particles having an average size inthe range from 6 nm to 200 nm, more preferably in the range from 7 to150 nm, very preferably in the range from 8 to 90 nm, more preferablystill in the range from 8 to 60 nm, most preferably in the range from 10to 25 nm. These particles may also be present in the form of gel or sol.The particles may, for example, have been alkali-stabilized in order toobtain better dispersion. An addition of boron for dispersing theinorganic compound in particle form was not necessary and has also notbeen used in the examples. It is preferred for relatively largeparticles to have a more platelet-shaped or elongate grain morphology.

[0044] In the case of the method of the invention it is also possible toadd at least one organic solvent. As organic solvent for the organicpolymers it is possible to use at least one water-miscible and/orwater-soluble alcohol, a glycol ether or N-methylpyrrolidone and/orwater—in the case of the use of a solvent mixture, a mixture inparticular of at least one long-chain alcohol, such as propylene glycol,an ester alcohol, a glycol ether and/or butanediol with water. In manycases, however, it is preferred to add only water, without any organicsolvent. The amount of organic solvent is preferably from 0.1 to 10% byweight, in particular from 0.25 to 5% by weight, very preferably from0.4 to 3% by weight. For strip production it is preferable to use onlywater and no organic solvent, apart possibly from small amounts ofalcohol.

[0045] In the case of the method of the invention it is possible to addas a lubricant, which may also serve as a forming agent, at least onewax selected from the group consisting of paraffins, polyethylenes, andpolypropylenes, especially an oxidized wax. It is particularlyadvantageous to employ the wax as an aqueous or as a cationically,anionically and/or sterically stabilized dispersion, since it can theneasily be held homogeneously distributed in the aqueous composition. Themelting point of the wax used as lubricant is preferably in the rangefrom 40 to 165° C., more preferably in the range from 50 to 160° C., inparticular in the range from 120 to 150° C. In addition to a lubricanthaving a melting point in the range from 120 to 165° C. it is especiallyadvantageous to add a lubricant having a melting point in the range from45 to 95° C. or having a glass transition temperature in the range from−20 to +60° C., particularly in amounts of from 2 to 30% by weight,preferably from 5 to 20% by weight, of the overall solids content. Sucha lubricant may also be used with advantage on its own. The at least onelubricant which may also at the same time be a forming agent ispreferably present in the aqueous composition in an amount in the rangefrom 0.1 to 25 g/L and with particular preference in an amount in therange from 1 to 15 g/L. The presence of wax is only advantageous,however, if the coating of the invention is a treatment layer, since ina pretreatment layer the presence of wax may be deleterious for thepainting operation. A lubricant and/or forming agent can be added inorder to reduce the friction coefficient of the coating, especiallyduring forming. The substances recommended for this purpose includeparaffin, polyethylene, and oxidized polyethylene.

[0046] The acid groups of the synthetic resin and/or of the polymer mayhave been neutralized with ammonia, with amines—especiallyalkanolamines—such as, for example, morpholine, dimethylethanolamine,diethyl-ethanolamine, or triethanolamine and/or with alkali metalcompounds such as sodium hydroxide, for example.

[0047] The inventive solution or dispersion for coating may comprise atleast one corrosion inhibitor, especially based on amine(s). Thecorrosion inhibitor may contain at least one organic group and/or atleast one amino group. It may be an organic compound or an ammoniumcompound, in particular an amine or an amino compound, such as, forexample, comprise a TPA-amine complex, a phosphonate, a polyasparticacid, a thiourea, a Zr ammonium carbonate, benzotriazole, a tannin, anelectrically conductive polymer such as a polyaniline, for example,and/or derivatives thereof. This inhibitor may be at least onealkanolamine, preferably a long-chain alkanolamine, and/or at least onethiol. It is preferably not readily volatile at room temperature.Further, it may be advantageous if it is readily soluble in water and/orreadily dispersible in water, in particular at more than 20 g/L.Particular preference is given inter alia to alkylaminoethanols such asdimethylaminoethanol or to complexes based on a TPA amine such asN-ethylmorpholine complex with 4-methyl-γ-oxo-benzynebutanoic acid. Thiscorrosion inhibitor can be added in order to bring about a relativelyrobust inhibition of corrosion or to reinforce corrosion inhibitionstill further. It is particularly advantageous if ungalvanized steelsurfaces, especially cold-rolled steel (CRS), are to be coated. It ispreferably present in the aqueous composition in an amount in the rangefrom 0.1 to 50 g/L and more preferably in an amount in the range from 1to 20 g/L or, preferably, in an amount in the range from 0.01 to 5 partsby weight, more preferably in the range from 0.03 to 2 parts by weight,very preferably in the range from 0.05 to 1.2 parts by weight, based on100 parts by weight of water.

[0048] The ratio of the amounts of organic film former to amounts oflubricant in the aqueous composition (bath solution) can vary withinwide limits; in particular it can be ³ 2:1. Preferably this ratio lieswithin a range from 3:1 to 50:1, more preferably within a range from10:1 to 20:1.

[0049] The ratio of the amounts of organic film former to amounts of atleast one corrosion inhibitor in the aqueous composition (bath solution)can vary within wide ranges; in particular it can be ² 500:1. Preferablythis ratio is situated within a range from 5:1 to 400:1, more preferablywithin a range from 10:1 to 100:1.

[0050] The aqueous composition of the invention is preferably free fromaddition of free fluoride, of complex fluoride such as hexafluorotitanicacid or hexafluorozirconic acid, for example, and/or of fluoride boundin other ways.

[0051] Particularly advantageous compositions of the invention includeat least one copolymer based for example onacrylic-polyester-polyurethane, styrene and/or ethylene-acrylic as filmformers, at least one inorganic compound in particle form based inparticular on alumina, aluminum phosphite, iron oxide, iron phosphite,mica, lanthanide oxide(s) based for example on cerium oxide, molybdenumsulfide, graphite, carbon black, silicate, silica, colloidal silica,zinc oxide and/or zirconium oxide, at least one crosslinking agent, atleast one corrosion inhibitor and, where appropriate, further additionssuch as, inter alia, at least one silane/polysiloxane. The particleshaving a relatively high or high electrical conductivity may forapplication for welding also be selected such that they have an averageparticle size such that they protrude somewhat more, where appropriate,from the layer of the invention.

[0052] The inventive solution or dispersion for coating may comprise atleast one crosslinking agent based in particular on a basic compound inorder to produce resistance to aggressive media such as chemicals andeffects of weathering and also to mechanical stresses and in order toensure color stability particularly in the case of aluminum andaluminum-containing surfaces in conditions of high atmospheric humidityor wet-room exposure and to prevent darkening. Particularly advantageouscrosslinking agents are those based on titanium, hafnium and/orzirconium and those based on carbonate or ammonium carbonate, especiallybased on titanium and/or zirconium. It is preferably present in theaqueous composition in an amount in the range from 0.1 to 30 g/L andmore preferably in an amount in the range from 1 to 10 g/L or,preferably, in an amount in the range from 0.01 to 3 parts by weight,more preferably in the range from 0.1 to 1 parts by weight, verypreferably in the range from 0.2 to 0.6 parts by weight, based on 100parts by weight of water.

[0053] Moreover it is advantageous to add at least one wetting agent inorder to allow the wet film to be applied uniformly in its areal extentand in its layer thickness and also imperviously and without defects. Inprinciple, numerous wetting agents are suitable for this purpose,preferably acrylates, silanes, polysiloxanes, long-chain alcohols, whichlower the surface tension of the aqueous composition. In many cases itwill be necessary to add a defoamer. For better filming of the polymericparticles of the aqueous composition during drying it is possible touse, particularly as a temporary plasticizer of the polymer particles, along-chain alcohol, preferably a butanediol, based in particular ontriethylene glycol or tripropylene glycol. The additives which areuseful here and can be added are basically known to the skilled worker.

[0054] The aqueous composition may where appropriate comprise in eachcase at least one biocide, defoamer, wetting agent and/or at least onefurther additive such as is typical for paints or paintlikecompositions.

[0055] Metallic Substrates or Metallically Coated Substrates, TheirTreatment/Pretreatment, Their Coating with the Paintlike Coating, andthe Further Course of the Method:

[0056] The term “clean metallic surface” here denotes an uncleanedmetallic, e.g., freshly galvanized, surface on which no cleaning isneeded, or a freshly cleaned surface.

[0057] In the case of the method of the invention the aqueouscomposition can be applied by roller application, flowcoating,knifecoating, squirting, spraying, brushing or dipping, includingdipping at elevated temperature of the aqueous composition and, whereappropriate, by subsequent squeezing off, for example, using a roll.

[0058] The aqueous composition may have a pH in the range from 0.5 to12, preferably in the range from 1 to 6 or from 7 to 9, more preferablyin the range from 1.5 to 4 or from 6 to 10.5, depending on whether themethod is carried out in the acidic or rather in the basic range.

[0059] The aqueous composition may be applied in particular at atemperature in the range from 5 to 50° C. to the metallic surface,preferably in the range from 10 to 40° C., more preferably in the rangefrom 18 to 25° C., or at from 30 to 95° C.

[0060] In the case of the method of the invention the metallic surfacewhen the coating is applied may be held at temperatures in the rangefrom 5 to 120° C., preferably in the range from 10 to 60° C., verypreferably from 18 to 25° C, or at from 50 to 120° C.

[0061] In the case of films of this kind final drying may last manydays, whereas the essential drying can be completed in just a fewseconds. Under certain circumstances, curing may take several weeksuntil the ultimate state of drying and state of cure has been reached,possibly accompanied by filming and/or cross-linking. If necessary, thestate of cure can additionally be accelerated or intensified byacceleration of the crosslinking by radiation, for example, with UVradiation or by heating, and/or else by adding, for example, compoundscontaining free NCO groups and reacting them with the carboxyl groups ofthe carboxyl-containing polymers.

[0062] Additionally, the coated metallic surface can be dried at atemperature in the range from 20 to 400° C., preferably in the rangefrom 40 to 120° C. or in the range from 140 to 350° C., very preferablyat from 60 to 100° C. or at from 160 to 300° C. PMT (peak metaltemperature), depending on the chemical composition of the organic filmformers. The necessary residence time during drying is substantiallyinversely proportional to the drying temperature: in the case ofstrip-form material, for example, from 1 to 3 s at 100° C. or from 1 to20 s at 250° C. in accordance with the chemical composition of thesynthetic resins or polymers, or 30 min at 20° C., while polyesterresins containing free carboxyl groups in combination withmelamine-formaldehyde resins cannot be dried at temperatures below 120°C. Moreover, depending among other things on their wall thickness,coated moldings must be dried for significantly longer. Particularlysuitable for drying is drying equipment based on air circulation,induction, infrared and/or microwaves.

[0063] The layer thickness of the coating of the invention is situatedpreferably in the range from 0.1 to 6 μm, more preferably in the rangefrom 0.2 to 5 μm, very preferably in the range from 0.4 to 4 μm, inparticular in the range from 0.7 to 2 μm.

[0064] The fractional areas of the delaminated area in the T-bend teston moldings (metal sheets) coated with coil coating material arepreferably up to 8%, more preferably up to 5%, very preferably up to 2%,but with the best values situated at approximately 0%, so that thennormally only cracks occur. For this purpose it is possible withpreference to use a coil coating material based on silicone-polyester,especially for comparative testing in tests which are typical for coatedcoils. The freedom from cracks or the size of the cracks here is alsosubstantially dependent on the nature of the coating material used,however.

[0065] In the context of the coating of strips, the coated strips can bewound to form a coil, where appropriate after cooling to a temperaturein the range from 40 to 70° C.

[0066] To the partly or fully dried and/or cured film it is possible toapply in each case at least one coating comprising varnish, paintlikecoating, polymer, paint, functional plastics coatings, adhesives and/oradhesive backing such as, for example, a self-adhesive sheet; inparticular, a wet coating, a powder coating, a plastics coating, anadhesive inter alia for film coating.

[0067] The metal parts coated inventively with the aid of the aqueouscomposition, especially strips or strip sections, can be formed,painted, coated with polymers such as PVC, for example, printed, coatedwith adhesive, hot-soldered, welded and/or joined to one another or toother elements by clinching or other joining techniques. These processesare known fundamentally for the coating of metallic strips orarchitectural applications. Generally, painting or other coating iscarried out first, followed by forming. If the coating of the inventionis painted or coated with plastic, soldered and/or welded connectionscannot be produced without the coatings being removed, at least locally.

[0068] The part with a metallic surface that is coated inventively withthe aqueous composition may be a wire, a wire winding, a wire mesh, asteel strip, a metal sheet, a panel, a shield, a vehicle body or part ofa vehicle body, a part of a vehicle, trailer, recreational vehicle ormissile, a cover, a casing, a lamp, a light, a traffic light element, afurniture item or furniture element, an element of a householdappliance, a frame, a profile, a molding of complex geometry, aguideboard element, radiator element or fencing element, a bumper, apart made from or with at least one pipe and/or one profile, a windowframe, door frame or cycle frame, or a small part such as, for example,a bolt, nut, flange, spring or a spectacle frame. The substrates coatedin accordance with the invention may be used in particular in thevehicle, air travel or space travel industry, in architecture or inappliance construction, especially for household appliances.

[0069] The method of the invention represents an alternative to theaforementioned chromate-rich processes and also to acid-free oracid-containing processes, particularly in the area of the surfacepretreatment of metal strip prior to painting, and in comparison withthese processes provides results of similar quality in terms ofcorrosion control and paint adhesion. The coatings of the invention maybe substantially or entirely free not only of chromium(VI) compounds butalso of chromium(III) compounds, without losing quality as a result.

[0070] The method of the invention can, however, also be employedadvantageously in the presence of at least one chromium compound ifcorrosion control is to be maintained across a wide spectrum and withhigh security, especially with regard to damage to the protective layerthat may be caused by mechanical stresses during transport, storage, andassembly of the substrates treated with the treatment liquid of theinvention on the substrate surface. In that case it is possible to add,for example, sodium dichromate, potassium dichromate and/or ammoniumdichromate. The amount of chromium(VI) compounds in that case ispreferably from 0.01 to 100 g/L, more preferably from 0.1 to 30 g/L.

[0071] Furthermore, it is possible to employ the method of the inventionfor treating the conventionally cleaned metal surface without asubsequent aftertreatment such as rinsing with water or with a suitableafter-rinse solution. The method of the invention is particularlysuitable for the application of the treatment solution by means ofsqueeze rolls or by means of what is called a rollcoater, in which casethe treatment solution can be dried immediately following applicationwithout further method steps in between (dry-in-place technology). As aresult, the method is simplified considerably as compared, for example,with conventional spraying or dipping processes, particularly thoseinvolving subsequent rinse operations, such as chromating orzinc-phosphating, and only very small quantities of rinsing water forplant cleaning are produced after the end of operation, since there isno need for a rinsing operation following application, which alsoconstitutes an advantage over the established chromium-free processeswhich operate in a spraying process with after-rinse solutions. Thisrinsing water can be added to a new batch of the bath solution.

[0072] It is readily possible here to use the polymeric, optionallychromate-free, coating of the invention without the precedingapplication of an additional pretreatment layer, so that outstandinglong-term protection of the metallic surfaces and especially on AlSi,ZnAl such as Galfan®, AlZn such as Galvalume®, ZnFe, ZnNi such asGalvanneal®, and other Zn alloys as metallic coatings or Al or Zncoatings is possible and can be achieved by applying apolymer-containing coating. Furthermore, the coating of the inventionhas also proven effective in cases of metallic surfaces highlysusceptible to corrosion, such as those of iron alloys and steel alloys,particularly in the case of cold-rolled steel, in which case it isadvantageous to add at least one corrosion inhibitor to the aqueouscomposition. This allows the formation of flash rust to be preventedduring the drying of the treatment liquid on cold-rolled steel (CRS).

[0073] Thus it is possible to achieve a cost-effective andenvironmentally friendly corrosion control which in addition does notrequire a costly UV cure but instead is adequately curable solely withthe drying and filming or with the “common chemical” cure, oftenreferred to as “thermal crosslinking”. In some cases, however, it may beof interest to obtain a harder coating rapidly in a defined operatingstep. In that case it can be advantageous to add at least onephotoinitiator and to select at least one UV-curable polymer componentin order to obtain partial crosslinking on the basis of actinicradiation, especially UV radiation. The coating of the invention canthen be brought to cure partly by actinic radiation and partly by dryingand filming or by thermal crosslinking. This may be of importanceparticularly in the case of application to high-speed strip plants orfor the first crosslinking (i.e., curing). The fraction of the UVcrosslinking, as it is termed, can be from 0 to 50% of the totalpossible curing, preferably from 10 to 40%.

[0074] The polymeric and substantially or entirely chromate-free coatingof the invention also has the advantage that, particularly with athickness in the range from 0.5 to 3 μm, it is transparent and light incolor, so that the metallic nature and the typical structure, forexample, of a galvanized or of a Galvalume® surface remains visibleexactly and without alteration, or virtually without alteration, throughthe coating. Moreover, such thin coatings can still be welded withoutproblems.

[0075] Furthermore, the polymeric coating of the invention is readilydeformable, since it can be made so that, after coating, drying, andcuring, and also, where appropriate, for a period of time, it is in arelatively plastic state rather than a hard, brittle state.

[0076] The polymer-containing coating of the invention can be readilyovercoated with the majority of paints or plastics. Thepolymer-containing coating of the invention can be afterpainted orcoated with plastic such as PVC by application techniques such as, forexample, powder coating, wet painting, flowcoating, rolling, brushing ordipping. In the majority of cases, the cured coatings thereby producedwhich are applied to the polymer-containing coating of the invention,and for which in many cases it is also possible to apply two or threepaint or plastics layers, have a total thickness in the range from 5 upto 1500 μm.

[0077] The polymeric coating of the invention can also be backed in amold with foam, polyurethane insulating foam for example, withoutproblems in order to produce two-sheet sandwich elements, or can bebonded effectively using the usual construction adhesives such as areemployed, for example, in vehicle construction.

[0078] The coatings of the invention can be used in particular as primerlayers. With or without at least one pretreatment layer appliedbeforehand, they are outstandingly suitable. This pretreatment layer maythen be, inter alia, a coating based on phosphate, especially ZnMnNiphosphate, or based on phosphonate, silane and/or a mixture based onfluoride complex, corrosion inhibitor, phosphate, polymer and/or finelydivided particles.

[0079] The coatings of the invention produce pretreatment layers orprimer layers which together with the subsequently applied paintproduced a coating system which is equal to the best chromium-containingcoating systems.

[0080] The coatings of the invention are very inexpensive,environmentally friendly, and well suited to industrial use.

[0081] It was surprising that with a synthetic resin coating of theinvention, despite a layer thickness of only about 0.5 to 1.5 μm, it waspossible to produce an extremely high-quality chromium-free film whichdoes not discolor the substrate surfaces and which provides excellentcorrosion control. Further, it was surprising that simply the additionof finely divided particles resulted in a significant improvement incorrosion resistance. Very surprisingly, the basic crosslinking agent,especially together with a corrosion inhibitor, improved the corrosioncontrol significantly once again.

[0082] As compared with the processes described and/or practiced todate, the method of the invention has the further advantage that onaluminum-rich or on an aluminum-alloy-coated substrate—particularly inthe case of a substrate of steel—it causes no darkening of the substratesurface and also no milky white dulling of the substrate surface, and socan be used for the decorative design of buildings and/or parts ofbuildings without additional painting to impart color. The esthetics ofthe metal surface remain unchanged.

[0083] Use of Anticorrosion Layers and/or of Paintlike or Paint Layers:

[0084] If anticorrosion layers are applied in the context of the methodof the invention, this may be one to four layers, which can all beapplied to one another directly, one after the other. It is preferred toapply at least two or three anticorrosion layers in succession. Each ofthese layers is preferably an anticorrosion layer selected from thegroup consisting of coatings based in each case on iron-cobalt,nickel-cobalt, at least one fluoride, at least one complex fluoride,especially tetrafluoride and/or hexafluoride, an organic hydroxycompound, a phosphate, a phosphonate, a polymer, a rare earth compoundcomprising at least one rare earth element, including lanthanum andyttrium, a silane/siloxane, a silicate, cations of aluminum, magnesiumand/or at least one transition metal selected from the group consistingof chromium, iron, hafnium, cobalt, manganese, molybdenum, nickel,titanium, tungsten, and zirconium, or is a coating based onnanoparticles, but it is also possible where appropriate for at leastone further anticorrosion layer to be applied. In this case the at leastone further anticorrosion layer may be applied, as desired, beforeand/or after the first, second or third anticorrosion layer. It can beimportant to apply more than one anticorrosion layer (pretreatmentlayer), since the subsequent paintlike or paint layers are often kept sothin in comparison to the prior art paint systems that the corrosioncontrol requirements must be heightened accordingly.

[0085] With the method of the invention it is possible, for example, toapply the first anticorrosion layer in a drying method and the secondanticorrosion layer in a drying method or rinse method.

[0086] A drying method is a no-rinse method in which a film of liquid isapplied to the optionally precoated strip. A rinse method is a method ofcoating which produces a coating by reaction, in particular duringspraying or dipping, and in which the coating is subsequently rinsed inorder to remove excess chemicals, and in which the coating, finally, isdried. It is preferred to apply coatings based, for example, on zincphosphate and/or manganese phosphate, usually containing a small amountof nickel, by a no-rinse method. It is, however, also possible for manyother kinds of coating-com-dried.

[0087] With this method it is possible, for example, to apply the firstanticorrosion layer by a rinse method and the second anticorrosion layerby a drying method or rinse method.

[0088] In this case, the second anticorrosion layer can be applied in anafterrinsing step, in particular after the first anticorrosion layer hasbeen applied beforehand on a galvanizing line.

[0089] The galvanizing line may preferably operate electrolyticgalvanizing, electrolytic alloy galvanizing, hot galvanizing, hot-dipgalvanizing and/or hot-dip alloy galvanizing. Coatings applied here maybe, inter alia, pure zinc, zinc with a purity in the range from 98 to99.9%, aluminum-zinc alloys, zinc-aluminum alloys, and zinc-nickelalloys.

[0090] The second anticorrosion layer may be applied here by a dryingmethod, in particular after the first anticorrosion layer has beenapplied beforehand on a galvanizing line. Galvanizing on the galvanizingline may preferably comprise electrolytic galvanizing, hot galvanizing,hot-dip galvanizing and/or hot-dip alloy galvanizing.

[0091] With the method of the invention it is possible to coat surfacesof aluminum, iron, cobalt, copper, magnesium, nickel, titanium, tin orzinc or alloys comprising aluminum, iron, cobalt, copper, magnesium,nickel, titanium, tin and/or zinc, especially electrolyticallygalvanized or hot-dip galvanized surfaces. The following are preferredmetallic coatings on the metallic strips: electrolytically galvanizedsteel, hot-dip-galvanized steel, hot-dip alloy-galvanized steel, andaluminum alloy coated with pure aluminum.

[0092] The pretreatment prior to painting is preferably chromium-free orsubstantially chromium-free, in particular chromium-free to the extentthat no chromium is deliberately added. The pretreatment solutions alsopreferably contain little or no cobalt, copper, nickel and/or otherheavy metals, respectively.

[0093] With the method of the invention it is possible to coat with atleast one liquid, solution or suspension which is substantially orentirely free from chromium compounds before coating with at least onepaint and/or with at least one paintlike polymer-containing layer whichcomprises polymers, copolymers, crosspolymers, oligomers, phosphonates,silanes and/or siloxanes. Substantially free from chromium may here meanwithout deliberate addition of a chromium compound. The term “liquid”also embraces solvent-free compounds or mixtures in liquid form.

[0094] This method may also be distinguished by the fact that no lead,cadmium, chromium, cobalt, copper and/or nickel is added to the liquid,solution or suspension for the first and/or second anticorrosion layer.Heavy metals which are added, such as lead, cadmium, chromium, cobalt,copper and/or nickel, are generally added only in minimal amounts.

[0095] Because of the at least one anticorrosion layer, it is possiblein the case of the method of the invention, as compared with the stateof the art on the priority date, to forego at least one of the otherwisecustomary pretreatment layers, paint layers and/or paintlikepolymer-containing layers, in particular a pretreatment layer and apaint layer (see Tables 2A-J relating to variants A ff).

[0096] In this case the liquid, solution or suspension for at least oneof the anticorrosion layers and/or paintlike polymer-containing layersmay comprise, in addition to water, at least one organic film formerwith at least one water-soluble or water-dispersed polymer, copolymer,block copolymer, crosspolymer, monomer, oligomer, derivative(s) thereof,mixture(s) thereof and/or addition copolymer(s) thereof. The fraction ofthese organic compounds in a layer is preferably in the range from 60 to99.8% by weight, based on the solids content.

[0097] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers and/or paint-like polymer-containinglayers may comprise, in addition to water, a total content of cations,tetra-fluoro complexes and/or hexafluoro complexes of cations selectedfrom the group consisting of titanium, zirconium, hafnium, silicon,aluminum, and boron and/or free or otherwise-bound fluorine, inparticular from 0.1 to 15 g/L complex fluoride based on F₆, preferablyfrom 0.5 to 8 g/L complex fluoride based on F₆, or from 0.1 to 1000 mg/Lof free fluorine. The fraction of these compounds in a layer ispreferably in the range from 5 to 99.9% by weight.

[0098] In this context, the liquid, solution and/or suspension for atleast one of the anticorrosion layers and/or paintlikepolymer-containing layers may comprise, in addition to water, a totalcontent of free fluorine or fluorine not attached to tetrafluoro orhexafluoro complexes, in particular from 0.1 to 1000 mg/L calculated asfree fluorine, preferably from 0.5 to 200 mg/L, more preferably from 1to 150 mg/L.

[0099] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise, in addition towater, at least one inorganic compound in particle form having anaverage particle diameter, measured under a scanning electronmicroscope, in the range from 0.003 up to 1 μm diameter, preferably inthe range from 0.005 up to 0.2 μm diameter, based in particular onAl₂O₃, BaSO₄, rare earth oxide(s), at least one other rare earthcompound, SiO₂, silicate, TiO₂, Y₂O₃, Zn, ZnO and/or ZrO₂, preferably inan amount in the range from 0.1 to 80 g/L, more preferably in an amountin the range from 1 to 50 g/L, very preferably in an amount in the rangefrom 2 to 30 g/L. The fraction of these compounds in particle form in alayer is preferably in the range from 5 to 90% by weight, morepreferably in the range from 10 to 50% by weight. Electricallyconductive particles can be used as well, such as iron oxide, ironphosphite, molybdenum compounds such as molybdenum sulfide, graphiteand/or carbon black, for example, and/or it is also possible to use anaddition of conductive polymers if the metal sheets are to be joined,where appropriate by welding. These anti-corrosion layers are preferablyfree of elemental zinc.

[0100] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anti-corrosion layers, paintlayers or paintlike polymer-containing layers may comprise at least onecorrosion inhibitor. The corrosion inhibitor may contain at least oneorganic group and/or at least one amino group. It can be an organiccompound or an ammonium compound, in particular an amine or an aminocompound, such as, for example, an alkanolamine, a TPA-amine complex, aphosphonate, a polyaspartic acid, a thiourea, a Zr ammonium carbonate,benzotriazole, a tannin, an electrically conductive polymer such as apolyaniline, for example, and/or contain derivatives thereof. Inparticular it is selected from the group consisting of organic phosphatecompounds, phosphonate compounds, organic morpholine and thio compounds,aluminates, manganates, titanates, and zirconates, preferably ofalkylmorpholine complexes, organic Al, Mn, Ti and/or Zr compoundsespecially of the olefinically unsaturated carboxylic acids, forexample, ammonium salt of carboxylic acids such as chelated lactic acidtitanate, triethanolamine titanate or triethanolamine zirconate,Zr-4-methyl-γ-oxo-benzyne-butanoic acid, aluminum zirconium carboxylate,alkoxypropenolatotitanate or alkoxypropenolatozirconate, titaniumacetate and/or zirconium acetate and/or derivatives thereof, Ti/Zrammonium carbonate. The fraction of these compounds in a layer ispreferably in the range from 5 to 40% by weight.

[0101] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers or paintlikepolymer-containing layers may comprise at least one compound for theneutralization, in particular the slow neutralization, of comparativelyacidic mixtures and/or for the corrosion control of unprotected ordamaged portions of the metallic surface, based preferably on carbonateor hydroxy-carbonate or conductive polymers, more preferably at leastone basic compound with a layer structure such as, for example,Al-containing hydroxy-carbonate hydrate (hydrotalcite). The fraction ofthese compounds in a layer is preferably in the range from 3 to 30% byweight.

[0102] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may in addition to water comprise at least onesilane and/or siloxane, calculated as silane, in particular in an amountin the range from 0.1 to 50 g/L, preferably in an amount in the rangefrom 1 to 30 g/L.

[0103] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may in addition to water and/or at least oneorganic solvent comprise at least one silane and/or siloxane, calculatedas silane, in particular in an amount in the range from 51 to 1300 g/L.

[0104] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may where appropriate in addition to waterand/or at least one organic solvent comprise at least one silane and/orsiloxane, calculated as silane, in particular in an amount in the rangefrom 0.1 to 1600 g/L, preferably in an amount in the range from 100 to1500 g/L.

[0105] The silane may be an acyloxysilane, an alkylsilane, analkyltrialkoxysilane, an aminosilane, an aminoalkylsilane, anaminopropyltrialkoxysilane, a bis-silylsilane, an epoxysilane, afluoroalkylsilane, a glycidyloxysilane such as, for example, aglycidyloxytrialkoxysilane, an isocyanatosilane, a mercaptosilane, a(meth)acrylatosilane, a mono-silyl-silane, a multi-silyl-silane, abis(trialkoxysilylpropyl)amine, a bis(trialkoxysilyl)ethane, asulfur-containing silane, a bis(trialkoxysilyl)propyltetrasulfane, aureidosilane such as, for example, a (ureidopropyltrialkoxy)silaneand/or a vinylsilane, in particular a vinyltrialkoxysilane and/or avinyltriacetoxysilane. It can be, for example, at least one silane in amixture with up to 8% by weight, based on the silane content, of atleast one alcohol such as methanol, ethanol and/or propanol, preferablyup to 5% by weight, more preferably up to 1% by weight, very preferablyup to 0.5% by weight, in the presence or absence of inorganic particles,in particular in a mixture of at least one aminosilane such as, forexample, bis-amino-silane with at least one alkoxysilane such as, forexample, trialkoxysilylpropyltetrasulfane or a vinylsilane and abis-silyl-aminosilane or a bis-silyl-polysulfur-silane and/or abis-silyl-aminosilane or an amino silane and a multi-silyl-functionalsilane.

[0106] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise an organic filmformer in the form of a solution, dispersion, emulsion, microemulsionand/or suspension.

[0107] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise as organic film former at leastone synthetic resin, in particular at least one synthetic resin based onacrylate, ethylene, polyester, polyurethane, silicone-polyester,epoxide, phenol, styrene, styrene-butadiene, urea-formaldehyde, theirderivatives, copolymers, block copolymers, crosspolymers, monomers,oligomers, polymers, mixtures and/or addition copolymers. As a genericterm for all of these variants of synthetic resins and theirderivatives, copolymers, block copolymers, crosspolymers, monomers,oligomers, polymers, mixtures, and addition copolymers, the term“polymer” is used here, in particular for the paintlike layers as well.

[0108] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise as organic film former asynthetic resin mixture and/or addition copolymer comprising syntheticresin based on acrylate, ethylene, urea-formaldehyde, polyester,poly-urethane, styrene and/or styrene-butadiene and/or theirderivatives, copolymers, crosspolymers, oligomers, polymers, mixturesand/or addition copolymers, from which an organic film is formed duringor after the emission of water and other volatile constituents.

[0109] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise as organic film former syntheticresins and/or polymers, copolymers, block copolymers, crosspolymers,monomers, oligomers, polymers, mixtures and/or addition copolymersand/or their derivatives based on acrylate, polyethyleneimine,polyurethane, polyvinyl alcohol, polyvinylphenol, polyvinylpyrrolidoneand/or poly-aspartic acid, especially copolymers with aphosphorus-containing vinyl compound.

[0110] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise a synthetic resin whose acidnumber is in the range from 5 to 250. The acid number is preferably inthe range from 10 to 140, more preferably in the range from 15 to 100.

[0111] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise synthetic resins and/or polymers,copolymers, block copolymers, crosspolymers, monomers, oligomers,polymers, mixtures and/or addition copolymers and/or derivatives thereofwhose molecular weights are in the range of at least 1000 u, preferablyof at least 5000 u or of up to 500 000 u, more preferably in the rangefrom 20 000 to 200 000 u.

[0112] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise synthetic resins and/or polymers,copolymers, block copolymers, crosspolymers, monomers, oligomers,polymers, mixtures and/or addition copolymers and/or derivativesthereof, in particular based inter alia on pyrrolidone(s), in particularfrom 0.1 to 500 g/L, preferably from 0.5 to 30 or from 80 to 250 g/L.

[0113] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise an organic film former whose pHin an aqueous formulation without addition of further compounds is inthe range from 1 to 12, preferably in the range from 2 to 10, morepreferably in the range from 2.5 to 9.

[0114] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise an organic film former whichcontains only water-soluble synthetic resins and/or polymers,copolymers, block copolymers, crosspolymers, monomers, oligomers,polymers, mixtures and/or addition copolymers and/or their derivatives,particularly those which are stable in solutions with pH levels ≦5.

[0115] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise an organic film former whosesynthetic resin and/or polymers, copolymers, block copolymers,crosspolymers, monomers, oligomers, polymers, mixtures and/or additioncopolymers and/or their derivatives contain carboxyl groups.

[0116] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise an organic film former in whichthe acid groups of the synthetic resins and/or polymers, copolymers,block copolymers, crosspolymers, monomers, oligomers, polymers, mixturesand/or addition copolymers and/or their derivatives have been stabilizedwith ammonia, with amines such as morpholine, dimethylethanolamine,diethylethanolamine or triethanolamine, for example, and/or with alkalimetal compounds such as sodium hydroxide, for example.

[0117] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprise from 0.1 to 200 g/Land preferably from 0.3 to 50 g/L of the organic film former, inparticular from 0.6 to 20 g/L.

[0118] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers can comprise from 100 to 2000 g/L andpreferably from 300 to 1800 g/L of the organic film former, inparticular from 800 to 1400 g/L.

[0119] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may include a monomerfraction, in particular in the region of at least 5% by weight,preferably of at least 20% by weight, more preferably of at least 40% byweight. In this context, especially with a high fraction of monomers, itis possible, where appropriate, for the fraction of water and/or organicsolvent to be reduced and in particular to be less than 10% by weight;in certain circumstances it may even be entirely or substantially freefrom water and/or organic solvent.

[0120] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise from 0.1 to 50g/L of cations, tetrafluoro complexes and/or hexa-fluoro complexes ofcations selected from the group consisting of titanium, zirconium,hafnium, silicon, aluminum, and boron, preferably hexafluoro complexesof titanium, zirconium and/or silicon preferably a coating of 2 to 20g/L.

[0121] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise at least one organometalliccompound, particularly containing titanium and/or zirconium. Theseorgano-metallic compounds are often corrosion inhibitors and often alsoadhesion promoters at the same time.

[0122] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may include at least onesilane and/or siloxane calculated as silane in the aqueous composition,preferably in a range from 0.2 to 40 g/L, more preferably in a rangefrom-0.5 to 10 g/L.

[0123] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise at least one partly hydrolyzedsilane, at least one wholly hydrolyzed silane and/or at least onesiloxane.

[0124] In the course of the curing of the coating, siloxanes are formedfrom the silanes. It is also possible, however, to add correspondingsiloxanes. The silanes/siloxanes may be used either alone, in a mixture,for example, with at least one fluoride complex, or else together withpolymers.

[0125] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise at least one partly hydrolyzedand/or nonhydrolyzed silane, in particular in the case of a silanecontent of more than 100 g/L, more preferably in the case of a silanecontent of more than 1000 g/L.

[0126] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise in each case at least oneacyloxysilane, alkylsilane, aminosilane, bis-silyl-silane, epoxysilane,fluoro-alkylsilane, glycidyloxysilane, isocyanatosilane, mercaptosilane,(meth)acrylatosilane, mono-silyl-silane, multi-silyl-silane,sulfur-containing silane, ureidosilane, vinylsilane and/or at least onecorresponding siloxane.

[0127] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may have added to it asinorganic compound in particle form a finely divided powder, adispersion or a suspension such as, for example, a carbonate, oxide,silicate or sulfate, especially colloidal or amorphous particles.

[0128] In this context it is possible for the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers to have added to it asinorganic compound in particle form particles having an average size inthe range from 4 nm to 150 nm, in particular in the range from 10 to 120nm. The average size of the electrically conducting particles of awelding primer may be situated within the range from 0.02 to 15 μm.

[0129] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may have added to it as inorganic compound inparticle form particles based on at least one compound of aluminum,barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zincand/or zirconium.

[0130] In this context, to the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise from 0.1 to 300 g/L, preferablyfrom 0.2 to 60 g/L, of the at least one inorganic compound in particleform.

[0131] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may as organic solvent forthe organic polymers be used at least one water-miscible and/orwater-soluble alcohol, one glycol ether and/or one pyrrolidone such as,for example, N-methylpyrrolidone and/or water; where a solvent mixtureis used, it is in particular a mixture of at least one long-chainalcohol, such as propylene glycol, for example, an ester alcohol, aglycol ether and/or butanediol with water, but preferably only waterwithout organic solvent.

[0132] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anti-corrosion layers, paintlayers and/or paintlike polymer-containing layers may comprise organicsolvent in an amount in the range from 0.1 to 10% by weight.

[0133] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise as lubricant atleast one wax selected from the group consisting of paraffins,polyethylenes, and polypropylenes, in particular an oxidized wax. Theamount of waxes in a layer is preferably in the range from 0.1 to 20% byweight.

[0134] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers may comprise a wax lubricant whose meltingpoint is in the range from 40 to 160° C., preferably from 0.1 to 100g/L, more preferably from 20 to 40 g/L or from 0.1 to 10 g/L, verypreferably 0.4 to 6 g/L, for example, a crystalline polyethylene wax.

[0135] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise at least onerare earth element compound, in particular at least one compoundselected from the group consisting of chloride, nitrate, sulfate,sulfamate, and complexes, for example, with a halogen or with anaminocarboxylic acid, in particular complexes with EDTA, NTA or HEDTA,in which context scandium, yttrium, and lanthanum are also regarded asbeing rare earth elements.

[0136] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers and/or paintlike polymer-containinglayers may comprise a rare earth element compound of and/or with cerium,in particular in a mixture with other rare earth elements, for example,at least partly based on mixed metal. The amount of cerium compound in alayer is preferably in the range from 0.1 to 99% by weight, morepreferably in the range from 25 to 95% by weight. The at least one rareearth element compound is used in the aqueous solution preferably in anamount of from 1 to 80 g/L together with an amount in the region of atleast 10 mg/L of chloride, with an amount of peroxide in the range from1 to 50 g/L, calculated as H₂O₂, and with an amount of at least onecation selected from main group 5 or 6 of the periodic table of theelements, in particular of bismuth ions, in the range from 0.001 to 1g/L. The amount of the at least one rare earth element compound in theaqueous solution is preferably from 5 to 25 g/L together with an amountin the region of not more than 500 mg/L of chloride, with an amount ofperoxide in the range from 5 to 25 g/L, calculated as H₂O₂, and with anamount of at least one cation selected from main group 5 or 6 of theperiodic table of the elements, in particular of bismuth ions, in therange from 0.01 to 0.3 g/L.

[0137] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise at least oneoxidizing agent, in particular a peroxide, at least one acceleratorand/or at least one catalyst, preferably a compound and/or ions of Bi,Cu and/or Zn.

[0138] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise at least onecompound selected from the group of the mono-, bis-, and multi-silanes,especially:

[0139] mono-silanes of the general formula SiX_(m)Y_(4-m)

[0140] with m=1 to 3, preferably m=2 to 3,

[0141] with X=alkoxy, especially methoxy, ethoxy and/or propoxy, and

[0142] with Y as a functional organic group selected from the groupconsisting of acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl,glycidyloxy, urea, isocyanate, mercapto, methacrylate and/or vinyland/or derivatives thereof,

[0143] bis-silanes of the general formulaY_(3-p)X_(p)—Si-Z-Si-X_(n)Y_(3-n)

[0144] with p and n=1 to 3, identical or different,

[0145] with X=alkoxy, especially methoxy, ethoxy and/or propoxy, and

[0146] with Y as a functional organic group selected from the groupconsisting of acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl,glycidyloxy, urea, isocyanate, mercapto, methacrylate and/or vinyland/or derivatives thereof,

[0147] with Z selected from the group of C_(n)H_(2n) with n=2 to 20, ineach case branched or unbranched, of singly unsaturated alkyl chains ofthe general formula C_(n)H_(2n-2) with n=2 to 20, in each case branchedor unbranched, of doubly and/or multiply unsaturated alkyl compounds ofthe general formulae C_(n)H_(2n-4) with n=4 to 20, in each case branchedor unbranched, C_(n)H_(2n-6) with n=6 to 20, in each case branched orunbranched, or C_(n)H_(2n-8) with n=8 to 20, in each case branched orunbranched, of ketones, monoalkylamines, NH, and sulfur S_(q) with q=1to 20,

[0148] multi-silanes of the general formulaY_(3-p)X_(p)—Si-Z′-Si—X_(n)Y_(3-n)

[0149] with p and n=1 to 3, identical or different,

[0150] with X=alkoxy, especially methoxy, ethoxy and/or propoxy, and

[0151] with Y as a functional organic group selected from the groupconsisting of acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl,glycidyloxy, urea, isocyanate, mercapto, methacrylate,mono/bis/multi-silyl and vinyl and/or derivatives thereof,

[0152] and with Z′=N—Si—X_(r)Y_(3−r) with r=1 to 3 or sulfur S_(q) withq=1 to 20,

[0153] multi-silanes of the general formulaY_(3−p)X_(p)—Si-Z″-Si—X_(n)Y_(3−n)

[0154] with p and n=1 to 3, identical or different,

[0155] with X=alkoxy, especially methoxy, ethoxy and/or propoxy, and

[0156] with Y as a functional organic group selected from the groupconsisting of acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl,glycidyloxy, urea, isocyanate, mercapto, methacrylatemono/bis/multi-silyl and vinyl and/or derivatives thereof,

[0157] and with Z″=—R—C[(SiX_(s)Y_(3−s))(SiX_(t)Y_(3−t))]—R′— or sulfurS_(q) with q=1 to 20,

[0158] with s and t=1 to 3, identical or different,

[0159] with R and R′, identical or different, selected from the group ofC_(n)H_(2n) with n=2 to 20, in each case branched or unbranched, ofsingly unsaturated alkyl chains of the general formula C_(n)H_(2n-2)with n=2 to 20, in each case branched or unbranched, of doubly and/ormultiply unsaturated alkyl compounds of the general formulaeC_(n)H_(2n-4) with n=4 to 20, in each case branched or unbranched,C_(n)H_(2n-6) with n=6 to 20, in each case branched or unbranched, orC_(n)H₂₋₈ with n=8 to 20, in each case branched or unbranched, ofketones, monoalkylamines, NH,

[0160] it being possible for the silanes in each case to be present inhydrolyzed, partly hydrolyzed and/or nonhydrolyzed form in a solution,emulsion and/or suspension.

[0161] In this context, the total content of silanes and/or siloxanesper layer can be preferably, on the one hand, in the range from 0.01 to20% by weight, on the other hand, preferably, in the range from 60 to99.9% by weight.

[0162] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers may compriseat least one compound of the type XYZ, X*Y*Z* and/or X*Y*Z*Y*X*,

[0163] where Y is an organic group having 2 to 50 carbon atoms

[0164] where X and Z, identical or different, are an OH, SH, NH₂, NHR′,CN, CH═CH₂, OCN, CONHOH, COOR′, acrylamide, epoxide, CH₂═CR″—COO, COOH,HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH) (OR′)PO, (OH) (OR′)PO₂, SiH₃ and/oran Si(OH)₃ group,

[0165] where R′ is an alkyl group having 1 to 4 carbon atoms,

[0166] where R″ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms, where the groups X and Z are each attached to the group Yin the terminal position thereof,

[0167] where Y* is an organic group having 1 to 30 carbon atoms,

[0168] where X* and Z*, identical or different, are an OH, SH, NH₂,NHR′, CN, CH═CH₂, OCN, CONHOH, COOR′, acrylamide, epoxide, CH₂═CR″—COO,COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH) (OR′)PO, (OH) (OR′)PO₂, SiH₃,Si(OH)₃, >N—CH₂—PO(OH)₂ and/or an —N—[CH₂—PO(OH)₂]₂ group,

[0169] where R′ is an alkyl group having 1 to 4 carbon atoms, and

[0170] where R″ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms.

[0171] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers may comprise at least one compound ofthe type XYZ, where X is a COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂,(OH)(OR′)PO or (OH)(OR′)PO₂ group,

[0172] where Y is an organic group R containing 2 to 50 carbon atoms, ofwhich at least 60% of these carbon atoms are present in the form of CH₂groups,

[0173] where Z is an OH, SH, NH₂, NHR′, CN, CH═CH₂, OCN, epoxy,CH═CR″—COOH, acrylamide, COOH, (OH)₂PO, (OH)₂PO₂, (OH)(OR′)PO or(OH)(OR′)PO₂ group, where R′ is an alkyl group having 1 to 4 carbonatoms,

[0174] and where R″ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms, preferably in total from 0.01 to 10 g/L, preferably from0.05 to 5 g/L, very preferably from 0.08 to 2 g/L.

[0175] In this context, the compound of type XYZ, X*Y*Z* and/orX*Y*Z*Y*X* may be suitable for forming self-arranging molecules, whichmay shape a layer of these self-arranging molecules particularly on themetallic surface, preferably a monomolecular layer.

[0176] In this context, the liquid, solution or suspension for at leastone of the anticorrosion layers may comprise at least one of thefollowing compounds of type XYZ, X*Y*Z* and/or X*Y*Z*Y*X*:

[0177] 1-phosphonic acid-12-mercaptododecane,

[0178] 1-phosphonic acid-12-(N-ethylaminododecane),

[0179] 1-phosphonic acid-12-dodecene,

[0180] p-xylylenediphosphonic acid,

[0181] 1,10-decanediphosphonic acid,

[0182] 1,12-dodecanediphosphonic acid,

[0183] 1,14-tetradecanediphosphonic acid,

[0184] 1-phosphoric acid-12-hydroxydodecane,

[0185] 1-phosphoric acid-12-(N-ethylamino)dodecane,

[0186] 1-phosphoric acid-12-dodecene,

[0187] 1-phosphoric acid-12-mercaptododecane,

[0188] 1,10-decanediphosphoric acid,

[0189] 1,12-dodecanephosphoric acid,

[0190] 1,14-tetradecanediphosphoric acid,

[0191] p,p′-biphenyldiphosphoric acid,

[0192] 1-phosphoric acid-12-acryloyldodecane,

[0193] 1,8-octanediphosphonic acid,

[0194] 1,6-hexanediphosphonic acid,

[0195] 1,4-butanediphosphonic acid,

[0196] 1,8-octanediphosphoric acid,

[0197] 1,6-hexanediphosphoric acid,

[0198] 1,4-butanediphosphoric acid,

[0199] aminotrimethylenephosphonic acid,

[0200] ethylenediaminetetramethylenephosphonic acid,

[0201] hexamethylenediaminetetramethylenephosphonic acid,

[0202] diethylenetriaminepentamethylenephosphonic acid,

[0203] 2-phosphonobutane-1,2,4-tricarboxylic acid.

[0204] The amounts of compounds of these types in a layer is preferablyin the range from 50 to 100% by weight. In the case of the method of theinvention at least one of the liquids, solutions or suspensions for atleast one of the anticorrosion layers and/or paintlikepolymer-containing layers may comprise phosphate and zinc, whereappropriate also manganese, nickel and/or copper. The amounts ofphosphates in a layer is preferably in the range from 8 to 100% byweight, more preferably in the range from 20 to 95% by weight, verypreferably in the range from 60 to 90% by weight.

[0205] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers and/or paintlike polymer-containing layers may contain from 0.1to less than 100 g/L zinc ions, from 0.4 to 80 g/L manganese ions, up to12 g/L nickel ions, up to 100 g/L peroxide, calculated as H₂O₂, and from1 to 500 g/L phosphate ions, calculated as P₂O₅, and also, preferably,from 0.2 to less than 50 g/L of zinc ions, from 0.5 to 45 g/L manganeseions, and from 2 to 300 g/L phosphate ions, calculated as P₂O₅.

[0206] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers and/or paintlike polymer-containing layers may comprisephosphate, preferably based on Zn or ZnMn, where appropriate with nickelcontent.

[0207] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise phosphate, fluoride, tetrafluoride and/or hexafluoride.Preferably, however, phosphonate(s), which align themselves at leastpartially as self-arranging molecules on the metallic surface, andfluoride complexes with separate solutions in largely separate layersare formed.

[0208] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise phosphonate, tetrafluoride and/or hexafluoride.

[0209] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise an organic film former, fluoride, tetrafluoride, hexafluorideand/or at least one inorganic compound in particle form, and, whereappropriate, at least one silane.

[0210] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise an additive selected from the group consisting of organicbinders, biocides, defoamers, corrosion inhibitors, adhesion promoters,wetting agents, photoinitiators, and polymerization inhibitors.

[0211] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise at least one filler and/or one pigment, in particular at leastone electrically conductive pigment selected from the group consistingof dyes, color pigments, graphite, graphite-mica pigments, oxides suchas iron oxides, molybdenum compounds, phosphates, phosphides such asiron phosphides, carbon black and zinc. The amount of such compounds ina layer is preferably in the range of from 0.1 to 60% by weight, morepreferably in the range from 5 to 35% by weight.

[0212] In the case of the method of the invention an activatingtreatment can be applied prior to the application of an anticorrosionlayer, paint layer and/or paintlike polymer-containing layer, preferablyan activation based on titanium.

[0213] In the case of the method of the invention the application of ananticorrosion layer, paint layer or paintlike polymer-containing layermay be followed by application of an afterrinse and/or passivation,preferably an after-rinse solution based on rare earth compounds,complex fluorides, silanes, titanium compounds and/or zirconiumcompounds and/or a passivating solution based on rare earth compounds,complex fluorides, silanes, titanium compounds and/or zirconiumcompounds.

[0214] In the case of the method of the invention at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers maycomprise an organic film former which, following application to themetallic substrate, is cured by heat and/or actinic radiation, inparticular by electrons, UV and/or radiation in the visible lightregion.

[0215] In the case of the method of the invention at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers may be only partly cured prior to adhesive bonding, welding,and/or forming and not fully cured until after adhesive bonding, weldingand/or forming, the first curing before adhesive bonding, welding and/orforming taking place by actinic radiation—in particular by electrons, UVand/or radiation in the visible light region—and the second curingtaking place after adhesive bonding, welding and/or forming, preferablythermally, in particular by radiant heat and/or hot air. The first curetakes place preferably nonthermally, in particular by UV radiation,since there are normally no ovens for heating present in the metal stripline, in particular in the strip galavanizing line. The second curepreferably takes place thermally, especially when the metal sheet is tobe aftercured at the same time. The second cure, however, takes placepreferably by means of actinic radiation, in particular by UV radiation,since this is often accompanied by better through-curing than by meansof thermal crosslinking alone. Furthermore, it is also possible toutilize more than one type of cure in each of the curing steps. For thesake of simplicity, actinic radiation is referred to in thisspecification as UV radiation and the associated cure is termed UVcuring.

[0216] In the case of the method of the invention, the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may have a pH in the rangefrom 0.5 to 12, preferably in the range from to 1 to 11, more preferablyin the range from 2 to 10.

[0217] In the case of the method of the invention, the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may be applied to therespective surface at a temperature in the range from 5 to 95° C.,preferably in the range from 5 to 50° C., very preferably in the rangefrom 10 to 40° C.

[0218] In this context, the substrate and/or the respective surface maybe held during application of the anticorrosion layer(s) at temperaturesin the range from 5 to 120° C. In the case of the first coating this maybe the metallic surface. The first or second anticorrosion layer orbasecoat may be applied preferably in a temperature range from 10 to 50°C.

[0219] The coated metallic surface may in this case be dried at atemperature in the range from 20 to 400° C. PMT (peak metaltemperature). The first and second anticorrosion layer may be appliedpreferably in a temperature range of 15 to 100° C., the basecoat inparticular in a temperature range from 15 to 270° C.

[0220] In the case of the method of the invention the coated strips maybe cut up or wound to a coil, where appropriate after cooling to atemperature in the range from 10 to 70° C.

[0221] Method of one of the above claims, characterized in that thedivided strips, after pressing, cutting and/or punching, are coated inthe edge region with a temporarily applied coating to be removed againor with a permanently protecting coating, e.g., at least one coatingbased on dry lubricant, phosphate, hexa-fluoride, paintlike coatingand/or paint.

[0222] In the case of the method of the invention the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers can be applied by rolling,flowcoating, knifecoating, spraying, squirting, brushing or dipping and,where appropriate, by subsequent squeezing off with a roll.

[0223] In the case of the method of the invention the coating applied ineach case with the liquid, solution or suspension for at least one ofthe anticorrosion layers, paint layers and/or paintlikepolymer-containing layers can be adjusted to a layer weight in the rangefrom 0.0005 mg/m² to 150 g/m², preferably in the range from 0.0008 mg/m²to 30 g/m², more preferably in the range from 0.001 mg/m² to 10 g/m², inparticular in the range from 1 to 6 g/m².

[0224] In the case of the method of the invention at least one coatingof paint or of a paintlike, polymer-containing coating can be applied ineach case to the partly or fully cured film, the first paint layer orpaintlike polymer-containing layer being able to be composed essentiallyof primer, a thinly—in the range from 0.1 to 10 μm, preferably in therange from 0.15 to 6 μm,, more preferably in the range from 0.2 to 4μm—organically applied, polymer-containing material (called a permanentcoating), a reaction primer, a shop primer or a wash primer. For thepurposes of this specification a reaction primer is a primer such as,for example, a coil coating primer, a primer as replacement for thecathodic dip coat, or a welding primer.

[0225] In the case of the method of the invention it is possible toapply in each case at least one coating of paint, a mixture of or withpolymers, varnish, adhesive and/or adhesive backing to the at leastpartly painted strip or the strip at least partly coated in a paintlikemanner with a polymer-containing layer, or to the at least partlypainted strip section or the strip section coated at least partly in apaintlike manner with a polymer-containing layer.

[0226] In the case of the method of the invention the clean or cleanedand, where appropriate, activated metallic surface may be contacted withthe liquid, solution or suspension for one of the anticorrosion layersand at least one film, which where appropriate may also containparticles, may be formed on the metallic surface, which is subsequentlydried and, where appropriate, additionally cured, the dried and, whereappropriate, also cured film possibly having in each case a thickness inthe range from 0.01 to 100 μm, in particular a film with a thickness inthe range from 5 up to 50 μm, more preferably in the range from 8 up to30 μm. Particles which can be used include pigments, especially colorpigments or white pigments, metal particles such as zinc particles,fillers of all kinds such as, for example, chalk, oxides such asalumina, talc or silicates, carbon particles, and nanoparticles.

[0227] In this context at least one paint layer may be applied asundercoat or one paintlike polymer-containing layer as pretreatmentprimer, primer, primer as replacement of the cathodic dip coat,lubricating primer, reaction primer, welding primer and/or wash primer,where appropriate instead of an undercoat. The overall paint system mayin certain circumstances amount to up to 300 μm, generally up to 120 μm,often up to 90 μm, occasionally up to only 70 μm, if using more than onepaint and/or paintlike layer.

[0228] In this context, at least one of the paint layers and/orpaintlike polymer-containing layers may be cured by heat and/or actinicradiation, in particular by UV radiation.

[0229] In the case of the method of the invention the coated strips orstrip sections may be subjected to forming, painted, coated withpolymers such as PVC, for example, printed, bonded, hot soldered, weldedand/or joined with one another or with other elements by clinching orother joining techniques.

[0230] In the case of the coating of metallic strip the productionsequence may be that specified below, which indicates by way of examplethe sequence for steel sheets which are to be galvanized. Thismanufacturing sequence, where appropriate omitting the coating with ametal or with an alloy such as in the case of galvanizing, may also betransferred to other metallic substrates and used in the same way.

[0231] Table 1: Manufacturing Sequence Variants in the Coating of SteelSheet Which is to be Galvanized

[0232] 1. Electrolytic cleaning with a strong alkaline cleaner to cleanthe surface entirely of organic impurities such as fat and oil, forexample, and of other dirt.

[0233] 2. Rinsing with water in a rinsing cascade, final zone with fullydeionized water.

[0234] 3. Only in the case of electrolytic galvanizing: acid pickling:spray with water containing sulfuric acid, with a pH of 1 to 2.

[0235] 4. Galvanizing: hot-dip galvanizing by dipping in melt bath orelectrolytic galvanizing by dipping in a bath containing an aqueous zincsolution: coating with industrial-purity zinc, which may contain certainimpurities, particularly of aluminum and lead (HDG); coating with arelatively iron-rich or aluminum-rich zinc alloy such as Galvanneal®,Galfan® or Galvalume®.

[0236] 5. In the case of electrolytic galvanizing: following thedeposition of the galvanizing layer, acidic pickling to removeunevennesses in the galvanizing layer.

[0237] 6. Especially when phosphate layers are to be applied: coatingwith an activating solution based in particular on titanium.

[0238] 7. Optional application of a first anticorrosion layer, e.g., asprephosphating.

[0239] 8. Optional rinsing with water or, where appropriate, afterrinsesolution; after prephosphating, only water.

[0240] 9. Optional application of a second anticorrosion layer, e.g., analkaline Fe Co oxide layer.

[0241] 10. Optional rinsing with water.

[0242] 11. Optional application of a third anticorrosion layer, e.g.,based on hexafluoride.

[0243] 12. Optional rinsing with water.

[0244] 13. Optional application of a first paintlike coating.

[0245] 14. Optional UV irradiation for crosslinking the paintlikecoating.

[0246] 15. Optional heating at temperatures in the range from 50 to 160°C. for thermal crosslinking of the paintlike coating.

[0247] 16. Optional application of a second paintlike coating, referredto as the paint interlayer.

[0248] 17. Optional UV irradiation for crosslinking the second paintlikecoating.

[0249] 18. Optional heating at temperatures in the range from 50 to 160°C. for thermal crosslinking of the second paintlike coating.

[0250] 19. Optional application of a first paint layer as surfacer ortopcoat, modified where appropriate with a content of nanoparticles.

[0251] 20. Optional application of a second paint layer as surfacer ortopcoat, modified where appropriate with a content of nanoparticles.

[0252] 21. Optional application of a third paint layer as topcoat,modified where appropriate with a content of nanoparticles.

[0253] 22. Optional heating at temperatures in the range from 50 to 160°C. for thermal crosslinking (curing) of the paint layer(s).

[0254] 23. Optional UV irradiation for crosslinking the final paintlayer.

[0255] In the table below the abovementioned process steps—by way ofexample for steel sheet which is to be galvanized—are assigned to thepossible manufacturing lines, the specific sequences, and any agents tobe used therein. The assignment of particular process steps to themanufacturing line is, however, in each case only one of severalpossibilities. Manufacturing line Zn=galvanizing line. Manufacturingline CC=coil coating. Manufacturing line bodywork parts manufacture orbodywork manufacture or corresponding manufacturing line in aircraftconstruction or space travel industry=bod. Z=number of process stepswithout all possible intermediate steps which may be necessary, such aspickling, cleaning, activating, rinsing or afterrinsing, and/or drying,for example. These method variants apply very substantially in the sameway for other metallic materials as well, where appropriate withoutgalvanizing. TABLES 2A-J Variants of the assignment of process steps andmanufacturing lines in the case of steel sheet which is to begalvanized, disregarding intermediate steps Variants A Basis of theprincipal Line Z Process step agents Zn 1 galvanizing zinc, ZnFe, ZnAl 2pretreatment, rinse or chromate, Fe/Co/Ni no-rinse, optional afterrinseoxide, free fluoride, complex fluoride, phosphate, phosphonate, rareearths, silane, silicate and/or polymer CC 3 optional mild-alkalinecleaning 4 chromium-containing or chromate, Fe/Co/Ni chromium-freeoxide, free fluoride, pretreatment complex fluoride, phosphate,phosphonate rare earths, silane, silicate and/or polymer 5 basecoat coilcoating primer, lubricating or welding primer: UV curing and/orthermosetting CC or 6 optional paint bod interlayer 7 color coat 8clearcoat, optionally two layers bod 9 cutting, pressing and/or stamping10 optional (further) forming 11 optional joining such as clinching,bonding, for example 12 optional clearcoat Line Z Process step Principalagents Variants B Zn 1 galvanizing zinc, ZnFe, ZnAl 2 pretreatment,rinse or chromate, Fe/Co/Ni no-rinse, optional oxide, free fluoride,afterrinse complex fluoride, phosphate, phosphonate rare earths, silane,silicate and/or polymer CC 3 optional mild-alkaline cleaning 4 basecoat,optionally coil coating primer, with pretreatment lubricating primer orproperties welding primer: UV curing and/or thermosetting; chromate,free fluoride, complex fluoride, phosphate, phosphonate, rare earths,silane, silicate, corrosion inhibitor, pigment, polymer and/or wax CC or5 optional paint bod interlayer 6 color coat 7 clearcoat, optionally twolayers bod 8 cutting, pressing and/or stamping 9 optional (further)forming 10 optional joining such as clinching, bonding, for example 11optional clearcoat Variants C Zn 1 galvanizing zinc, ZnFe, ZnAl 2pretreatment, rinse or chromate, Fe/Co/Ni no-rinse, optional oxide, freefluoride, afterrinse complex fluoride, phosphate, phosphonate, rareearths, silane, silicate and/or polymer 3 basecoat, optionally coilcoating primer, with pretreatment lubricating primer or propertieswelding primer: UV curing and/or thermosetting; chromate, free fluoride,complex fluoride, phosphate, phosphonate, rare earths, silane, silicate,corrosion inhibitor, pigment, polymer and/or wax Zn* 4 optional paintinterlayer CC or 5 color coat bod 6 clearcoat, optionally two layers bod7 cutting, pressing and/or stamping 8 optional (further) forming 9optional joining such as clinching, bonding, for example 10 optionalclearcoat *where appropriate, alternatively on CC or bod Variants D Zn 1galvanizing zinc, ZnFe, ZnAl 2 pretreatment, rinse or chromate, Fe/Co/Nino-rinse, optional oxide, free fluoride, afterrinse complex fluoride,phosphate, phosphonate, rare earths, silane, silicate and/or polymer Znor 3 basecoat, optionally coil coating primer, CC with pretreatmentlubricating primer or properties welding primer: UV curing and/orthermosetting; chromate, free fluoride, complex fluoride, phosphate,phosphonate, rare earths, silane, silicate, corrosion inhibitor,pigment, polymer and/or wax CC or 4 optional paint bod interlayer 5color coat 6 clearcoat, optionally two layers bod 7 cutting, pressingand/or stamping 8 optional (further) forming 9 optional joining such asclinching, bonding, for example 10 optional clearcoat Variants E Zn 1galvanizing zinc, ZnFe, ZnAl 2 basecoat with coil coating primer,pretreatment properties lubricating primer or welding primer: UV curingand/or thermosetting; chromate, free fluoride, complex fluoride,phosphate, phosphonate, rare earths, silane, silicate, corrosioninhibitor, pigment, polymer and/or wax Zn* 3 optional paint interlayerCC or 4 color coat bod 5 clearcoat, optionally two layers bod 6 cutting,pressing and/or stamping 7 optional (further) forming 8 optional joiningsuch as clinching, bonding, for example 9 optional clearcoat *whereappropriate, alternatively on CC or bod Variants F Zn 1 galvanizingzinc, ZnFe, ZnAl 2 basecoat with coil coating primer, pretreatmentlubricating primer or properties, preferably welding primer: UVUV-curing curing and/or thermosetting; chromate, free fluoride, complexfluoride, phosphate, phosphonate, rare earths, silane, silicate,corrosion inhibitor, pigment, polymer and/or wax Zn* 3 optional paintinterlayer CC or 4 color coat, preferably bod UV-curing 5 clearcoat,preferably UV-curing bod 6 cutting, pressing and/or stamping 7 optional(further) forming 8 optional joining such as clinching, bonding, forexample 9 optional clearcoat, preferably UV-curing *where appropriate,alternatively on CC or bod Variants G Zn 1 galvanizing zinc, ZnFe, ZnAl2 pretreatment, rinse or chromate, Fe/Co/Ni no-rinse, optional oxide,free fluoride, afterrinse complex fluoride, phosphate, phosphonate, rareearths, silane, silicate and/or polymer 3 basecoat, optionally coilcoating primer, with pretreatment lubricating primer or properties,preferably welding primer: UV UV-curing curing and/or thermosetting;chromate, free fluoride, complex fluoride, phosphate, phosphonate, rareearths, silane, silicate, corrosion inhibitor, pigment, polymer and/orwax Zn* 4 optional paint interlayer bod 5 cutting, pressing and/orstamping 6 optional (further) forming 7 optional joining such asclinching, bonding, welding 8 color coat, preferably UV-curing 9clearcoat, optionally two layers, preferably UV-curing *whereappropriate, alternatively on CC or bod Variants H Zn 1 galvanizingzinc, ZnFe, ZnAl 2 basecoat with coil coating primer, pretreatmentlubricating primer or properties, preferably welding primer: UVUV-curing curing and/or thermosetting; chromate, free fluoride, complexfluoride, phosphate, phosphonate, rare earths, silane, silicate,corrosion inhibitor, pigment, polymer and/or wax Zn* 3 optional paintinterlayer bod 4 cutting, pressing and/or stamping 5 optional (further)forming 6 optional joining such as clinching, bonding, welding 7 colorcoat, preferably UV-curing 8 clearcoat, optionally two layers,preferably UV-curing *where appropriate, alternatively on CC or bodVariants J Zn 1 galvanizing zinc, ZnFe, ZnAl 2 basecoat with coilcoating primer, pretreatment properties lubricating primer or weldingprimer: UV curing and/or thermosetting; chromate, free fluoride, complexfluoride, phosphate, phosphonate, rare earths, silane, silicate,corrosion inhibitor, pigment, polymer and/or wax CC* 3 optional paintinterlayer 4 color coat, possibly UV-curing bod 5 cutting, pressingand/or stamping 6 optional (further) forming 7 optional joining such asclinching, bonding, welding 8 clearcoat, optionally two layers, possiblyUV-curing *could also run on other manufacturing lines such as Zn or bod

[0256] The table below illustrates which metallic substrates or metalliccoatings are coated onto substrates with at least one anticorrosionlayer and/or with at least one paintlike coating, and which compositionthe anticorrosion layer preferably possesses in this case. TABLE 3Correlation between preferred chemical bases of anticorrosion layers orcorresponding pretreatment solutions with metallic substrate or metalliccoating on a substrate, respectively: goes very well: ⊕, good: x,possible: •. 1., 2., and 3. show different coatings following oneanother. Chem. basis of Zn individual Al/ alloy, anticorrosion layers AlMg iron/ Stainless AlZn and/or their baths alloy alloy steel steel Znalloy Oxalate • • • ⊕ • • 1. oxalate, 2. chromate • • • ⊕ • • 1.oxalate, 2. polymer • • • ⊕ • • afterrinse solution 1. Fe/Co oxide, • ⊕⊕ 2. AlZrF₆ Ti and/or Zr hexa- ⊕ x ⊕ x ⊕ ⊕ fluoride Ti and/or Zr hexa- ⊕• ⊕ x ⊕ ⊕ fluoride with SiO₂ 1. Ti and/or Zr hexa- ⊕ x ⊕ • ⊕ ⊕ fluoride,2. silane(s) 1. Ti and/or Zr hexa- ⊕ • ⊕ • ⊕ ⊕ fluoride, 2. Mnphosphate 1. Ti and/or Zr hexa- ⊕ ⊕ • • • • fluoride, 2.phosphonate(s) 1. Ti and/or Zr hexa- ⊕ ⊕ ⊕ • x x fluoride, 2.phosphonate(s), 3. silane(s) Rare earth element(s) ⊕ • as nitrate(s)Rare earth element (s) ⊕ • • • • with Bi, peroxide and chloride Alphosphate x • x x x x Fe phosphate x • x x x x Mn phosphate ⊕ • ⊕ • ⊕ ⊕Zn phosphate ⊕ • ⊕ • ⊕ ⊕ ZnMn phosphate ⊕ • ⊕ • ⊕ ⊕ MnZn phosphate ⊕ • ⊕x ⊕ ⊕ 1. phosphate, ⊕ x ⊕ • ⊕ ⊕ 2. chromate afterrinse solution 1.phosphate, 2. Ti/ZrF₆ ⊕ x ⊕ • ⊕ ⊕ afterrinse solution 1. phosphate, ⊕ •⊕ • ⊕ ⊕ 2. polymer afterrinse solution Zn/Mn phosphate with x • ⊕ • ⊕ ⊕polymer and Ti/ZrF₆ Zn/Mn phosphate with x • ⊕ • ⊕ ⊕ polymer, Ti/ZrF₆,and nanoparticle Polymer • • • • • • Polymer with lubricant x • x x x xPolymer with ⊕ - • ⊕ - • ⊕ - • ⊕ - • ⊕ - • ⊕ - • nanoparticle* Polymerwith lubricant ⊕ ⊕ ⊕ ⊕ - x ⊕ ⊕ and nanoparticle* Polymer with lubricant,⊕ ⊕ ⊕ ⊕ - x ⊕ ⊕ corrosion inhibitor, and nanoparticle Polymer withlubricant, ⊕ ⊕ - • ⊕ ⊕ - x ⊕ ⊕ complex fluoride, corrosion inhibitor,and nanoparticle Polymer with lubricant, ⊕ ⊕ - • ⊕ ⊕ - x ⊕ ⊕ complexfluoride, corrosion inhihbitor, nanoparticle, and phosphate Phosphonate⊕ x x x Silane (s)/siloxane (s) ⊕ x ⊕ • ⊕ ⊕ Silane with Ti/ZrF₆ ⊕ x ⊕ ⊕⊕

[0257] The method of the invention is particularly advantageous since inthe short term at least some and in the medium term all of the chemicaland coatings technology operating steps can be moved from the automobileplant to the steelworks or aluminum/magnesium mill. There, thesesections of the method can run on high-speed manufacturing lines, inparticular on strip lines, and so can be utilized with a time saving,much more uniformly, more environmentally friendly, with savings ofchemicals, water, space, energy, and costs, and with higher quality.Correspondingly, the costs of the pretreated, painted and, whereappropriate, formed parts are much lower per fabricated square meter ofthe coated surface. Lower quantities of sludge are obtained in thisprocess than in the case of the mode of manufacturing to date,especially during pretreatment and painting. Indeed, the baths inquestion have much lower volumes. Instead of about 20 to 250 m³, atypical bath volume is now only 5 to 15 m³. While pretreatment andpainting take place at present in a large automobile plant usually with3000 to 5000 m²/h, a throughput of about 8000 to 30 000 m²/h can beachieved on strip lines. The overall time for cleaning and pretreatmentcan be lowered from 20 to 40 minutes to 15 to 30 seconds. The weight ofthe pretreatment coating can in some cases be lowered from 1.5 to 4 g/m²to about 0.01 to 2 g/m². The chemical consumption in the pretreatmentcan be lowered from 20 to 40 g/m² to 1 to 10 g/m². Instead of 15 to 40 gof sludge per m² of coated surface, now only 0 to 6 g per m² areproduced. The painting and baking time can be reduced from 120 to 180minutes to 0.1 to 2 minutes—for 2 layers of paint in each case. Thepaint consumption falls, for 3 paint layers with 200 to 300 g/m², to 80to 120 g/m² for 2 paint layers. The overall costs could fallapproximately by from 5 to 20% of the present overall costs per m² ofcoated surface.

[0258] It was surprising that with a synthetic resin coating accordingto the invention, despite a thickness of only about 0.2 μm, it waspossible to produce an extremely high-quality chromium-free film whichproduces extraordinarily firm adhesion of paint to the coating of theinvention. Furthermore, it was surprising that the addition of finelydivided particles resulted in a significant improvement in the adhesivestrength of the paint; an improvement in the corrosion resistance couldhave been hoped for as a result of the incorporation of the inorganicparticles, but an improvement in the paint adhesion strength wasunforeseeable.

[0259] If paint layers or paintlike layers can be applied on the stripand not as part of the parts or bodywork manufacturing operation, thecosts as compared with parts or bodywork manufacturing can be loweredsignificantly. Consequently, manufacturing on a strip, such as on a coilcoating line in the parts manufacture or bodywork manufacture operation,is to be preferred.

EXAMPLES

[0260] The examples described hereinbelow are intended to illustrate thesubject matter of the invention. The recorded concentrations andcompositions relate to the treatment solution itself and not to any morehighly concentrated batch solutions that may be used. All concentrationfigures are to be understood as solids fractions; that is, theconcentrations relate to the weight fractions of the effectivecomponents irrespective of whether the raw materials used were in diluteform, e.g., as aqueous solutions. In addition to the compositions setout below it may be necessary or desirable in commercial practice to addfurther additives or to adapt the amounts correspondingly: for example,either to raise the total amount of additions or, for example, to raisethe amount of the defoamer and/or of the leveling agent such as apolysiloxane, for example.

[0261] Synthetic resins used were a styrene acrylate having a glasstransition temperature in the range from 15 to 25° C. and having anaverage particle size in the range from 120 to 180 nm, anacrylic-polyester-polyurethane copolymer having a blocking point in therange from 140 to 180° C. and a glass transition temperature in therange from 20 to 60° C., an ethylene-acrylic copolymer having a meltingpoint in the range from 70 to 90° C., and an acrylic-modifiedcarboxyl-containing polyester in particular having a number of OH groupsin the range from 80 to 120 and having an acid number in the range from50 to 90, calculated based on the solid resin, and also with a hardeningoff—for example, by addition of hexamethoxymethylmelamine with an acidnumber less than 5. The styrene-butadiene copolymer has a glasstransition temperature in the range from −20 to +20° C. and an acidnumber of from 5 to 30; because of the presence of carboxyl groups thiscopolymer is additionally crosslinkable, for example, with melamineresins or with isocyanate-containing polymers. The copolymer based onepoxide acrylate has an acid number in the range from 10 to 18 and aglass transition temperature of between 25 and 40° C. This copolymer forthe coating in particular of steel gives the coating of the invention ahigher chemical stability, in particular in the basic range, andimproves the adhesion properties with respect to the metallic substrate.

[0262] The fumed silica has a BET value in the range from 90 to 130m²/g, the colloidal silica an average particle size in the range from 10to 20 nm. The melamine-formaldehyde was used with a crosslinking partnerfor the carboxyl-containing polyester resin. The oxidized polyethyleneserved as a lubricant and forming agent (wax) and had a melting point inthe range from 125 to 165° C. The polysiloxane used was a polyethermodified dimethylpolysiloxane and served as wetting and flow agent forthe wet film during application. As a combination of silanes withfunctional and nonfunctional character, a mixture of hydrolyzed silanesbased on 1,2-bis(triethoxysilyl)ethane and aminopropyltriethoxysilane isused. The defoamer was a mixture of hydrocarbons, hydrophobic silica,oxalated compounds, and nonionogenic emulsifiers. As a long-chainalcohol, a tripropylene glycol mono-n-butyl ether was used for filmforming. The ammonium zirconium carbonate serves as crosslinking agent.As corrosion inhibitor, one based on a TPA-amine complex was used. Aschromate additive, ammonium dichromate was chosen in certain cases.

[0263] A) (Pre-)Treatment of Galvalume® Steel Sheets:

Inventive Example 1

[0264] Steel sheets obtained from commercial cold-rolled andsubsequently alloy-galvanized steel strip with 55% AlZn (Galvalume®),which for protection purposes were oiled during storage, were first ofall degreased in an alkaline spray cleaner, rinsed with water, dried atelevated temperature, and then treated with the aqueous composition ofthe invention. A defined amount of the aqueous composition (bathsolution) was applied by means of a rollcoater so as to give a wet filmthickness of about 10 ml/m². The wet film was subsequently dried attemperatures in the range from 80 to 100° C. PMT, filmed, and cured. Thecomposition of the bath solution is set out in Table 4.

[0265] The constituents were mixed in the order stated and the pH of thesolution was subsequently adjusted to 8.2 by means of ammonia solution.Following application, the solution was dried in a forced air oven atabout 90° C. PMT (peak metal temperature). The steel sheets treated inthis way were subsequently tested for their corrosion control and theirmechanical properties.

Inventive Examples 2 to 13, 15 to 20, and 30, and Comparative Examples14, 1, 2 and 4

[0266] Alloy-zinc steel sheets were treated as described in example 1with the aqueous composition set out in Table 4 and were dried andtested. In the case of example 9, drying was carried out at 180° C. PMT.In the case of comparative example 14, no inorganic compound in particleform was added. In the case of inventive example 30, the compositioncorresponds to that of inventive example 11 apart from the absence ofwax. In the case of comparative example 4, steel sheets alloy-galvanizedon the basis of Galvalume® without subsequent treatment were used, forthe purpose of comparison with inventive examples 1 to 20. TABLE 4Composition of the bath liquids of all inventive and comparativeexamples: Amount in parts by weight/example I 1 I 2 I 3 I 4 I 5 I 6 I 7I 8 I 9 I 10 I 11 Water 100 100 100 100 100 100 100 100 100 100 100Styrene acrylate 6.40 6.40 1.00 1.00 1.00 2.00 1.80Acrylic-polyester-polyurethane 6.40 3.40 3.00 2.40 3.70 3.90 2.70 2.60copolymer Ethylene-acrylic copolymer 3.00 3.00 3.00 3.00 1.50 1.00 2.702.60 Carboxyl-containing polyester 5.70 Melamine-formaldehyde 0 .60Colloidal SiO₂ 10-20 nm 2.50 2.50 2.50 2.50 2.50 1.25 2.50 1.60 1.501.40 Fumed silica 2.50 Oxidized polyethylene 0.50 0.50 0.50 0.50 0.500.50 0.50 0.50 0.50 0.50 0.50 Polysiloxane 0.10 0.10 0.10 0.10 0.10 0.100.10 0.10 0.10 0.10 0.10 Combination of silanes 0.40 Defoamer 0.10 0.100.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Long-chain alcohol 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Ammonium Zr carbonate0.40 TPA-amine complex 0.10 Amount in parts by weight/example I 12 I 13C 14 I 15 I 16 I 17 I 18 I 19 I 20 C 1 C 2 Water 100 100 100 100 100 100100 100 100 100 100 Styrene acrylate 4.40 2.22 2.00 1.82 1.68 1.56 1.701.70 4.50 4.38 Acrylic-polyester-polyurethane 4.40 3.09 2.80 2.56 2.352.18 2.60 2.53 4.40 4.28 copolymer Ethylene-acrylic copolymer 2.60 2.603.09 2.80 2.56 2.35 2.18 2.60 2.53 Carboxyl-containing polyesterMelamine-formaldehyde Colloidal SiO₂ 10-20 nm 1.40 1.40 0.80 1.46 2.022.48 1.40 1.40 Fumed silica Oxidized polyethylene 0.50 0.50 0.50 0.500.50 0.50 0.50 0.50 0.50 0.50 0.50 Polysiloxane 0.10 0.10 0.10 0.10 0.100.10 0.10 0.10 0.10 0.10 0.10 Combination of silanes Defoamer 0.10 0.100.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Long-chain alcohol 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Ammonium Zr carbonate0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 TPA-amine complex 0.10 0.100.10 0.10 0.10 0.10 0.10 0.10 0.10 Ammonium dichromate 0.10 0.24 0.24Amount in parts by weight/example I 30 I 21 I 22 I 23 I 24 I 25 I 26 I27 I 28 I 29 C 9 Water 100 100 100 100 100 100 100 100 100 100 100Styrene acrylate 1.89 2.00 1.90 1.60 1.45 1.70 1.80 4.38Acrylic-polyester-polyurethane copolymer 2.74 2.70 2.70 2.65 2.45 2.552.60 4.28 Ethylene-acrylic copolymer 2.74 2.70 2.65 2.65 2.45 2.55 2.652.65 2.65 2.60 Carboxyl-containing styrene- 2.15 butadiene copolymer4.25 Carboxyl-containing polyester Melamine-formaldehydeEpoxide-acrylate copolymer 4.25 2.10 Colloidal SiO₂ 10-20 nm 1.47 1.401.37 1.32 1.27 1.28 1.32 1.321 1.32 1.40 Fumed silica Oxidizedpolyethylene 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50Polysiloxane 0.11 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10Combination of silanes Defoamer 0.11 0.10 0.10 0.10 0.10 0.10 0.10 0.100.10 0.10 0.10 Long-chain alcohol 0.42 0.40 0.40 0.40 0.40 0.40 0.400.40 0.40 0.40 0.40 Ammonium Zr carbonate 0.42 0.40 0.40 TPA-aminecomplex 0.11 0.10 0.28 0.48 0.68 0.88 0.48 0.48 0.48 0.10 Ammoniumdichromate 0.24

[0267] Results of the Tests on Galvalume® Sheets:

[0268] The dry layer add-on of the dried, filmed, cured, and, whereappropriate, also thermally cured polymer-containing coatings gave forall of the experiments—except in the case of comparative example 4—ineach case values in the range from 900 to 1100 mg/m². The dried filmshad a thickness in the range from 0.8 to 1 μm. All coatings according tothe invention with the exception of example 1 were transparent andcolorless and showed a slight silky luster, so that the opticalcharacter of the metallic surface remained visible with virtually nochange. In the case of example 1, the coating was milky white with afairly pronounced dulling effect. TABLE 5 Results of the corrosioncontrol tests Salt Salt spray Constant spray test condensation test ASTMconditions ASTM B117-73 test Stacking Stacking B117-73 edge DIN 50 017test areal test edge areal corrosion CC areal corrosion corrosioncorrosion after corrosion after after after 480 h in after >1680 h 28days 28 days 480 h in % mm in % in % in mm I 1 <50 30 20 100 fullycorroded I 2 40 30 20 100 fully corroded I 3 40 30 20 100 fully corrodedI 4 20 20 0 50 fully corroded I 5 20 20 0 40 20  I 6 20 20 0 40 20  I 720 20 0 40 20  I 8 15 20 0 30 20  I 9 5 30 0 0 5 I 10 20 20 0 30 5 I 110 12 0 0 2 I 12 0 12 0 0 2 I 13 0 12 0 0 2 C 14 100 fully 0 30 fullycorroded corroded I 15 5 16 0 30 5 I 16 0 12 0 0 2 I 17 5 16 0 10 5 I 1820 16 0 20 5 I 19 0 12 0 0 0 I 20 0 12 0 0 0 C 1 90 30 20 100 fullycorroded C 2 0 20 0 0 0 I 30 0 12 0 0 2 C 4 100 fully 100 100 fullycorroded corroded

[0269] In the case of comparative example 14 and inventive examples 15to 18 the amount of colloidal silica was raised continuously from zero.In the course of the corrosion tests it was found that an amount ofabout 1.46 parts by weight of colloidal silica in the case of example 16gave the best corrosion control for this test series (Table 5).

[0270] Using the composition of example 16, Galvalume® sheets werecoated with a film thickness of the dried coating of the invention ofabout 1 g/m² and were dried at different temperatures. These sheets werethen subjected to a salt spray test in accordance with ASTM B 117-73(Table 6). TABLE 6 Results for example 16 on Galvalume ® sheets dried atdifferent temperatures Salt spray Salt spray Salt spray Salt spray testASTM test ASTM test ASTM test ASTM B117-73 B117-73 B117-73 B117-73 arealareal areal areal corrosion corrosion corrosion corrosion Drying after72 h after 240 h after 480 h after 720 h temperature in % in % in % in % 20° C. 0.5 10 10 10  40° C. 0.5 10 10 10  60° C. 0 2.5 5 5  80° C. 0 00 5 100° C. 0 0 0 2.5 120° C. 0 0 0 2.5

[0271] For method variants in the case of the particularly good example16 it was found that the temperature for drying the aqueous compositionon Galvalume® sheet should be at least about 60° C. in order to provideparticularly good results in terms of corrosion control. With increasedtemperature, better film formation and crosslinking is achieved. TABLE 7Results of mechanical tests Mandrel bending test König with conicalmandrel pendulum from 3.2 mm to 38 mm hardness, to in diameter, to DIN53 157 DIN ISO 6860 Erichsen cupping test I 1 60 cracks < 1.5 mmunaffected I 2 80 cracks < 1.5 mm unaffected I 3 60 no cracks unaffectedI 4 60 no cracks unaffected I 5 60 no cracks unaffected I 6 60 no cracksunaffected I 7 70 no cracks unaffected I 8 80 no cracks unaffected I 9120 no cracks unaffected I 10 60 no cracks unaffected I 11 60 no cracksunaffected I 12 60 no cracks unaffected I 13 80 no cracks unaffected C14 40 no cracks unaffected I 15 50 no cracks unaffected I 16 60 nocracks unaffected I 17 60 no cracks unaffected I 18 60 no cracksunaffected I 19 60 no cracks unaffected I 20 60 no cracks unaffected C 160 no cracks unaffected C 2 60 no cracks unaffected I 30 60 no crackscracked, abrasion C 4 inapplicable inapplicable cracked, abrasion:worsethan C 3

[0272] The smallest values in the corrosion tests of Tables 5 and 6indicate the best results. The results of the tests of Table 7 also showmarked differences between the different polymeric coatings, especiallyin the stacking test. The best coatings according to the invention areat least equal to the chromate-containing coatings in terms of arealcorrosion resistance. However, in the case of addition of chromate aswell to the coatings according to the invention, the edge corrosion mayalso be regarded as at least equal to that of the chromate-containingproducts known to date.

[0273] The test known as the stacking test may serve, among otherthings, to test for formation of rust. With this accelerated test it ispossible to assess the corrosion control, for example, of treated stripsurfaces with regard to the influence of a hot moist atmosphere, such asmay occur, for example, during storage or transport through differentclimatic zones of a wound strip (i.e., a coil). For this purpose, ineach case 8 or 10 test sheets treated on both sides with the treatmentliquid and dried are cut in 80×80 mm format, for example using impactshears. The cut edges remain unprotected and untreated. The sheets mustbe planar and are stacked horizontally in such a way that the flash ofthe cut edges points in one direction. Using a burette, 1 ml of DI waterper 100 cm² of surface area is applied to the respective substratesurface between the metal sheets. The stack of sheets is then packedwatertight in PE film and welded shut, so that the DI water cannotevaporate or escape during the test. The sheet stack packed in this wayis stored in a test chamber to DIN 50 017 CC for a test period of 4weeks. An assessment is then made as to what kind of rust (red rust,black rust, white rust) has developed in the edge region and whatpercentage area is affected by the rust. An assessment is also made asto what kind of rust has developed over the entire surface area and ofhow great the percentage corroded area fraction on the treated sheetsurface is. Galvalume® sheets in this test exhibit first white or blackcorrosion and, like steel, if the aluminum-zinc alloy coating has beenconsumed or has been damaged right through to the steel sheet, exhibitred corrosion.

[0274] The pendulum hardness was averaged over 5 measurements in eachcase, the values being rounded up or down accordingly. The lower thependulum hardness, the softer the film and also, usually, the better theadhesion of the film to the metallic surface. However, cross-cutresults, which might characterize the adhesion, are not particularlyinformative in the case of such thin films. In the case of comparativeexample 14 in connection with inventive examples 15 to 18, an increasein hardness is apparent owing to the addition of SiO₂ particles.

[0275] The ductile properties of the coating of the invention were setso that the coating is neither too soft nor too hard for the mechanicalattack of the tools during forming. As a result, a substantiallyundamaged coating remains after the forming operation. Moreover, as aresult of these ductile properties, the cut edges are relatively wellprotected, since the coating does not fragment at the cut edges and insome cases is even drawn up at the cut edge, so that increased edgeprotection is achieved. Fragmentation of the coating of the inventionduring the production of metal sheet sections would cause contaminationof the forming tools, which can lead to unwanted markings on thesurfaces of the metal sheets in the course of the operating steps whichfollow the shaping operation. As a result of the optimized ductilebehavior, surprisingly, a slip behavior and friction behavior wasachieved which does not have very low values to start with and then avery rapid increase in the slip coefficient and friction coefficients,but instead allows extraordinarily long low levels of slip and frictionduring different operations following forming.

[0276] The mandrel bending test is evidence of the good flexibility andgood adhesion of the coating to the metallic substrate, and of itsoutstanding formability.

[0277] Forming was carried out with a cup-drawing machine from Erichsen,model 142-20, with a sheet holder force of 2500 kp and with a drawingforce of 2 Mp. From the Galvalume® sheet sections treated in accordancewith the invention, disks of 60 mm in diameter were punched, and weredrawn to hat-shaped cups with a brim generally about 15 to 17 mm indepth and with a cup diameter of about 35 mm. Without the addition of alubricant and/or forming agent such as wax, there was damage to thealuminum-zinc spangle in the regions of the internal radii of the cups,in some cases with extremely severe metallic abrasion. Adding even asmall amount of a lubricant and/or forming agent prevented this surfacedamage, and the brim (disk) was drawn together to diameters in theregion of about 48 mm. Without the addition of a lubricant and/orforming agent forming was adversely affected in that the brim (disk)reduced its diameter to a lesser extent than with said addition, forinstance, to diameters only in the region of about 58 mm. This diameteris partly also dependent on the time at which a crack appeared and thetime of the associated machine shutoff. At that point, the cups hadgenerally been drawn only to a depth of 5 to 10 mm. Additionally,without the addition of a lubricant and/or forming agent, there wasalways a crack, generally a very long crack, in the region of theexternal radius of the cup, as a result of which the middle deep-drawnarea of the cup stood up steeply to one side, as in the case of a partlyopened can. In the case of comparative example 14, in relation toexamples 15 to 18, there was no difference in the visual extent of thedrawn cups in terms of the large external diameter, of shapedevelopment, and of surface development. Nor did wetting of the surfacewith a copper sulfate solution, so that a reaction surface reddish brownto black in color could form at defects in the organic coating, owing tothe reaction of the zinc coating with the copper sulfate, indicate anydifferences between cups with a different SiO₂ particle content. Thegood forming properties therefore appear to derive from the presence oforganic substance, especially oxidized polyethylene, and are positivelyinfluenced by the presence of inorganic particles.

[0278] Metal sheets such as those coated in inventive example 11 weredried further at different temperature PMT, namely at room temperaturefor 72 hours, at 40° C., 60° C., 80° C., 100° C. or 120° C. for 5minutes in each case, and thereafter at room temperature for at least 70hours. No difference was apparent in the visible extent of the drawncups in terms of the large external diameter, of shape development, andof surface development, even after wetting with copper sulfate. In thecase of the salt spray test, however, it was found that, with thesubstrate sections treated in accordance with inventive example 11 whichhad been dried at a temperature of 20° C., 40° C. or 60° C. thecorrosion control achievable was no more than satisfactory, albeitimproving with increasing temperature. The corrosion control afforded bythe substrate sections treated with inventive example 11 and dried at atemperature of 80° C., 100° C. or 120° C. was found to be good and even,with increasing temperature, very good.

[0279] It is anticipated that the experiments performed on Galvalume®sheets and the results determined can be transferred to sheets providedwith AlSi, ZnAl, ZnFe, ZnNi, Al, and Zn coatings without changing theprocess parameters and lead to virtually identical results.

[0280] B) Treatment of Cold-Rolled Steel (CRS):

[0281] In the case of inventive examples 21 to 28 and with reference tocomparative examples 5 to 8, the text below addresses

[0282] 1. the increasing fraction of the corrosion inhibitor (examples21 to 25),

[0283] 2. examples 26 and 28 for styrene-butadiene copolymers as filmformers,

[0284] 3. examples 27 and 28 for epoxide copolymers as film formers,

[0285] 4. comparative examples 5 to 8 for steel in the untreated, oiled,alkali-phosphated or zinc-phosphated state.

[0286] In comparison to examples 1 to 20 of Galvalume® sheets, examples21 to 28 below are specifically intended for the pretreatment prior topainting or for the treatment in each case of cold-rolled steel (CRS).The objective is, as compared with the hitherto customary oiling of thesteel surfaces as temporary corrosion control, to use acorrosion-protectingly pretreated steel surface which, unlike the oilfilm, need no longer be removed before subsequent painting and as aresult provides possibly considerable advantages in terms of theenvironmental burden: the disposal of the corrosion control oil from thecleaning-product baths which are normally used prior to subsequentpainting is largely or completely unnecessary as a result, if indeed ithas not already been possible to do without these cleaning operationsentirely, since the surfaces have not been soiled and/or have not beenoiled during transport, storage and/or further processing of themetallic substrates.

[0287] As a primer-integrated pretreatment for producing paintedsurfaces of cold-rolled steel, the method of the invention is ofeconomic importance: in accordance with the invention, acorrosion-protecting treatment of the steel surface is proposed whichinitially offers corrosion control during transport, storage, andfurther processing of the steel surface and which subsequently is partof the overall paint system. Accordingly, success has been achieved indeveloping a pretreatment primer for steel.

Inventive Example 21

[0288] Steel sheets obtained from commercial cold-rolled steel strip ofgrade ST 1405, which had been oiled for the purpose of protection duringstorage, were first degreased in an alkaline spray cleaner, rinsed withwater, dried at elevated temperature, and then treated with the aqueouscomposition of the invention. A defined amount of the aqueouscomposition (bath solution) was applied by means of a rollcoater so asto give a wet film thickness of about 10 ml/m². The wet film wassubsequently dried at a temperature in the range from 80 to 100° C. PMT,filmed, and cured. The bath liquid had the composition indicated inTable 4.

Inventive Examples 22 to 28

[0289] As described in example 21, steel sheets were treated with thetreatment liquid set out in Table 4, dried, and tested.

Comparative Example 5

[0290] Steel sheets of grade ST 1405 without corrosion control treatmentwere subjected to a condensation cycling test to DIN 50 017 KFW (seeTable 8).

Comparative Example 6

[0291] Steel sheets of grade ST 1405 were treated with a commercial milloil. They were then subjected to a condensation cycling test to DIN 50017 KFW (see Table 8).

Comparative Example 7

[0292] Steel sheets obtained from commercial cold-rolled steel strip ofgrade ST 1405, which had been oiled for the purpose of protection duringstorage, were first degreased in an alkaline spray cleaner, rinsed withwater, dried at elevated temperature, and then treated with thecommercial alkali phosphating system Unibond® WH, giving a thickness ofabout 0.3 μm. They were then subjected to a condensation cycling-test toDIN 50 017 KFW (see Table 8).

Comparative Example 8

[0293] Steel sheets obtained from commercial cold-rolled steel strip ofgrade ST 1405, which had been oiled for the purpose of protection duringstorage, were first degreased in an alkaline spray cleaner, rinsed withwater, dried at elevated temperature, and then treated with thecommercial tricationic zinc phosphating system Gardobond® 101, such asis in use in general industry, giving a thickness of about 1.5 μm. Theywere then subjected to a condensation cycling test to DIN 50 017 KFW(see Table 8).

[0294] Results of the Tests on Treated Cold-Rolled Steel:

[0295] The films of the polymer-containing coatings of the invention,dried and thermally cured in the course of drying, showed a thickness inthe range from 0.8 to 1 μm. The coating of comparative examples 7 and 8exhibited a thickness of about 0.3 and 1.5 μm respectively. All coatingsaccording to the invention were transparent and colorless and exhibiteda slight silky gloss, so that the optical character of the metallicsurface remained visible with virtually no alteration. TABLE 8 Resultsof the corrosion control tests of examples 21 to 28 and of comparativeexamples 5 to 8 Conden- sation Areal Areal Areal Areal Areal cyclingcorrosion corrosion corrosion corrosion corrosion test to after afterafter after after DIN 50 017 1 cycle 3 cycles 5 cycles 7 cycles 10cycles JFW in % in % in % in % in % I 21 0 0 5 15 20 I 22 0 0 2 10 15 I23 0 0 0 2 5 I 24 0 0 0 0 0 I 25 0 0 0 0 0 I 26 0 0 0 0 0 I 27 0 0 0 0 0I 28 0 0 0 0 0 C 5 80 100 not not not applicable applicable applicable C6 5 20 30 40 60 C 7 30 70 100 not not applicable applicable C 8 20 30 60100 not applicable

[0296] TABLE 9 Results of the mechanical tests: Mandrel bending testwith conical mandrel from König pendulum 3.2 mm to 38 mm hardness to DINin diameter, to Erichsen 53 157 DIN ISO 6860 cupping test I 21 60 nocracks unaffected I 22 60 no cracks unaffected I 23 60 no cracksunaffected I 24 60 no cracks unaffected I 25 60 no cracks unaffected I26 50 no cracks unaffected I 27 70 no cracks unaffected I 28 55 nocracks unaffected

[0297] The results of the experiments of inventive examples 21 to 25show that an increased fraction of corrosion inhibitor brings about aperceptible improvement in corrosion control. From examples 26 to 28 itis clear that the addition of acrylate-epoxide copolymer or ofstyrene-butadiene copolymer instead of styrene acrylate oracrylic-polyester-polyurethane copolymer, respectively, brings aboutimproved adhesion to the substrate and an increased chemical resistance,particularly toward alkaline substances. In this context it was foundthat the corrosion resistance gives good or equally good results above aminimum level of at least one corrosion inhibitor. The coatings of theinventive examples 21 to 28 are outstandingly suitable for the formingof cold-rolled steel. The comparative examples 5 to 8 did not needtesting in this context, since their coatings are completely unsuitablefor forming operations.

[0298] In comparison with the oiled substrate surface withoutconventional corrosion control layer (C 6) and also in comparison to theso-called non-film-forming pre-treatment layer or film-formingpretreatment layer such as, for example, by means of alkali phosphating(C 7) or zinc phosphating (C 8), in which the pretreated sheets aresubsequently overpainted, the coatings of the invention have theadvantage in particular that an entirely adequate to satisfactorycorrosion control can be ensured by the protective layer of theinvention on surface regions difficult to access, or to accesscompletely, during painting if, for example, strip is coated inaccordance with the invention and only then is formed and, whereappropriate, subsequently painted. In comparison to the oiled substratesurface without a conventional corrosion protection layer and also incomparison to the so-called non-film-forming pretreatment layer orfilm-forming pretreatment layer such as, for example, by alkaliphosphating or zinc phosphating, which require overpainting, the methodof the invention also has the advantage of ensuring satisfactorycorrosion control even without painting, e.g., in the case ofarchitectural metal sheets in interior situations or in protectedsituations without relatively high humidity, e.g., installed under theroof.

[0299] The coatings corresponding to examples 21 to 28 are highlysuitable as a pretreatment layer prior to painting or a treatment layerfor cold-rolled steel (CRS), which after an appropriate storage time isprocessed further into shaped parts and then painted or which isprocessed to components without subsequent painting in interiorsituations and is therefore not exposed to the stresses which are usualas a result of outdoor weathering.

[0300] Owing to the synthetic resin combination with a high fraction ofepoxide-acrylate copolymer or styrene-butadiene copolymer, in outdoorsituations the coating corresponding to inventive examples 26 to 28 issuitable only as a pretreatment prior to subsequent coating and not aslong-term bright corrosion control in outdoor situations, since thiscoating is not sufficiently stable to the kind of TV radiation exposureexperienced in the course of outdoor weathering. In interior situationsthese coatings can be used, only where there is very low humidity, as atreatment without subsequent paint.

[0301] It is very surprising that, for use on particularlycorrosion-sensitive surfaces such as steel, for example, it was possibleto develop a polymer-containing coating which has an aqueous basis,which is free from or contains a relatively small amount of organicsolvents, which is able to dry, film, and normally undergo at leastpartial crosslinking at low temperature—below 120° C. PMT, in particularin the range from 60 to 80° C. PMT—and rapidly—in the case of striplines, within a period of 1 to 3 s or, in the case of parts coating bydipping, owing to the run-off edges, within a time of 5 to 10 minutes,in the case of parts spraying in a time of up to 5 minutes—whilenevertheless ensuring effective corrosion resistance. Preferably, suchcoatings of the invention on steel should have a layer weight of from0.8 to 2 g/m², corresponding to a layer thickness in the rangeapproximately from 0.7 to 2.5 μm.

[0302] C) (Pre-)Treatment of Magnesium Castings:

Inventive Example 29

[0303] Castings in the form of plates with a thickness of about 5 mm,consisting of the magnesium alloys AZ91D and AM50A, on the basis ofMgAlZn and MgAlMn respectively, were first degreased in an alkalinespray cleaner, rinsed with water, dried at elevated temperature, andsubsequently treated with the aqueous composition of the invention. Anamount of the aqueous composition (bath solution) was applied byimmersion in the treatment liquid so that the average wet film thicknesswas about 1 to 1.5 ml/m². Thereafter the wet film was dried at atemperature in the range from 80 to 100° C. PMT, filmed, and cured. Thebath solution had the composition in accordance with Table 4.

Comparative Example 9

[0304] In comparison to example 29 the composition of comparativeexample 2 (see Table 4) was applied by the method of example 29 toplates of the same magnesium alloys.

[0305] Results of the Tests on Magnesium Castings: TABLE 10 Results ofthe corrosion control tests Salt spray Salt spray Salt spray Constanttest test test Salt spray condensation ASTM ASTM ASTM test ASTM climatetest B117-73 B117-73 B117-73 B117-73 DIN 50 017 areal areal areal edgecorrosion CC areal corrosion corrosion corrosion after corrosion after120 h after 240 h after 480 h 480 h after 240 h in % in % in % in mm in% I 29 0 10 20 0 0 C 9 0 10 20 0 0

[0306] The determination of pendulum hardness of the coating accordingto the invention gave values of 60. Since, with a few exceptions,magnesium alloys cannot be subjected to deep-drawing, it was notpossible to carry out the mandrel bending test. The films of thepolymer-containing coatings of the invention, dried and thermally curedin the course of drying, showed an average thickness of about 1.2 μm.The coating of comparative example 9 had an average thickness of about1.2 μm. The coating of the invention was transparent and colorless andexhibited a slight silky gloss, so that the optical character of themetallic surface remained visible with virtually no alteration. Thechromium-free coating of the invention was equal in terms of corrosionresistance to a coating containing chromium and polymer.

[0307] D) (Pre-)Treatment of Galvalume® Steel Sheets and of GalvanizedSteel Sheets in Chromium-Free Multilayer Systems:

Inventive Example 30

[0308] Steel sheets which, starting from commercial cold-rolled steelstrip, were alloy-galvanized by coating with 55% AlZn (Galvalume®) orhot galvanized by immersion in zinc melt (HDG), and which thereafterwere oiled for the purpose of protection during storage, and cut, werefirst of all degreased in an alkaline spray cleaner, rinsed with water,dried at elevated temperature, and then treated with a first aqueouscomposition. Both types of steel sheet were investigated in parallelduring this experiment and during the related experiments. A definedamount of the aqueous composition (bath solution) was applied by meansof a rollcoater so as to give a wet film thickness of 10 ml/m². Attemperatures in the range from 80 to 100° C. PMT the wet film wassubsequently dried, filmed, and cured. The composition of the first bathsolution is given in Table 11.

[0309] Subsequently, after cooling to room temperature, a secondtreatment was carried out with a second, inventive aqueous composition.In this case, a defined amount of the aqueous composition of theinvention (bath solution) was applied with the aid of a rollcoater so asto give a wet film thickness of about 10 ml/m². Thereafter, attemperatures in the range from 80 to 100° C. PMT the wet film was dried,filmed, and cured. The composition of the second bath solution is givenin Table 11. TABLE 11 Composition of the bath liquids of all inventiveand comparative examples: Example Amount in parts by weight I 30 I 31 I32 I 33 I 34 I 35 Composition of the bath solution for treatment 1 Water100 100 100 100 100 100 Acrylic-polyester- 0.80 0.80 polyurethanecopolymer Ethylene-acrylic copolymer 0.80 1.60 1.60 0.80 0.80 ColloidalSiO₂ 10-20 nm 0.80 1.60 1.60 1.60 1.60 1.60 Polysiloxane 0.02 0.02 0.020.02 0.02 0.02 Defoamer 0.02 0.02 0.02 0.02 0.02 0.02 Ammonium Zrcarbonate 0.40 0.40 0.40 0.40 TPA-amine complex 0.10 0.10 0.10 0.10 0.100.10 Dry film thickness, nm 160 320 320 320 240 240 Composition of thebath solution for treatment 2 Water 100 100 100 100 100 100 Styreneacrylate 1.80 1.80 1.80 1.80 1.80 1.80 Acrylic-polyester- 2.60 2.60 2.602.60 2.60 2.60 polyurethane copolymer Ethylene-acrylic copolymer 2.602.60 2.60 2.60 2.60 2.60 Colloidal SiO₂ 10-20 nm 1.40 1.40 1.40 1.401.40 1.40 Oxidized polyethylene 0.50 0.50 0.50 0.50 0.50 0.50Polysiloxane 0.10 0.10 0.10 0.10 0.10 0.10 Defoamer 0.10 0.10 0.10 0.100.10 0.10 Long-chain alcohol 0.40 0.40 0.40 0.40 0.40 0.40 Ammonium Zrcarbonate 0.40 0.40 0.40 0.40 0.40 0.40 TPA-amine complex 0.10 0.10 0.100.10 0.10 0.10 Dry film thickness, nm 1000 1000 1000 1000 1000 1000Example Amount in parts by weight I 36 I 37 I 38 I 39 I 40 Compositionof the bath solution for treatment 1 Water 100 100 100 100 100 Silane0.80 1.60 2.40 Phosphonates 0.03 Mixture based on ZrF₆ and 0.07polyacrylic acid Dry film thickness, nm 80 160 240 <80 10 Composition ofthe bath solution for treatment 2 Water 100 100 100 100 100 Styreneacrylate 1.80 1.80 1.80 1.80 1.80 Acrylic-polyester- 2.60 2.60 2.60 2.602.60 polyurethane copolymer Ethylene-acrylic copolymer 2.60 2.60 2.602.60 2.60 Colloidal SiO₂ 10-20 nm 1.40 1.40 1.40 1.40 1.40 Oxidizedpolyethylene 0.50 0.50 0.50 0.50 0.50 Polysiloxane 0.10 0.10 0.10 0.100.10 Defoamer 0.10 0.10 0.10 0.10 0.10 Long-chain alcohol 0.40 0.40 0.400.40 0.40 Ammonium Zr carbonate 0.40 0.40 0.40 0.40 0.40 TPA-aminecomplex 0.10 0.10 0.10 0.10 0.10 Dry film thickness, nm 1000 1000 10001000 1000 Example Amount in parts by weight C 10 I 41 C 11 C 12 C 13Composition of the bath solution for treatment 1 Water 100 100 100 100100 Silane mixture 1.60 Phosphonates 0.03 Mixture based on ZrF₆ and 0.07polyacrylic acid Styrene acrylate 1.80 Acrylic-polyester- 0.80 2.60polyurethane copolymer Ethylene-acrylic copolymer 0.80 2.60 ColloidalSiO₂ 10-20 nm 1.60 1.40 Oxidized polyethylene 0.50 Polysiloxane 0.020.10 Defoamer 0.02 0.10 Long-chain alcohol 0.40 Ammonium Zr carbonate0.40 0.40 TPA-amine complex 0.10 Dry film thickness, nm 320 1000 160 16010 No second treatment

[0310] The applied dry film thickness is given approximately in eachcase.

Inventive Example 31 to 35

[0311] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid according to Table11, dried, and tested.

[0312] After cooling to room temperature, a second, inventive treatmentwas then carried out with the second bath solution corresponding toTable 11, as described in example 30.

Inventive Example 36

[0313] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted essentially of a mixture of 67% byweight 1,2-bis(triethoxysilyl)ethane and 33% by weightaminopropyltriethoxysilane, to which acetic acid (glacial acetic acid),technical-grade denatured methanol, and demineralized water were added.The silane content of the solution used was 0.8% by weight. The aceticacid served here to adapt the pH, the methanol content to facilitate thehydrolysis of the silanes. The dry film thickness was set by way of theconcentration of the solution.

[0314] In this case, drying produced a dry film of about 80 nm inthickness. After cooling to room temperature, a second, inventivetreatment was then carried out with a second bath solution, as describedin example 30.

Inventive Example 37

[0315] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted essentially of a mixture of 67% byweight 1,2-bis(triethoxysilyl)ethane and 33% by weightaminopropyltriethoxysilane, to which acetic acid (glacial acetic acid),technical-grade denatured methanol, and demineralized water were added.The silane content of the solution used was 1.6% by weight. The aceticacid served here to adapt the pH, the methanol content to facilitate thehydrolysis of the silanes. The dry film thickness was set by way of theconcentration of the solution.

[0316] In this case, drying produced a dry film of about 160 nm inthickness. After cooling to room temperature, a second, inventivetreatment was then carried out with a second bath solution in accordancewith Table 11, as described in example 30.

Inventive Example 38

[0317] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted essentially of a mixture of 67% byweight 1,2-bis(triethoxysilyl)ethane and 33% by weightaminopropyltriethoxysilane, to which acetic acid (glacial acetic acid),technical-grade denatured methanol, and demineralized water were added.The silane content of the solution used was 2.4% by weight. The aceticacid served here to adapt the pH, the methanol content to facilitate thehydrolysis of the silanes. The dry film thickness was set by way of theconcentration of the solution.

[0318] In this case, drying produced a dry film of about 240 nm inthickness. After cooling to room temperature, a second, inventivetreatment was then carried out with a second bath solution in accordancewith Table 11, as described in example 30.

Inventive Example 39

[0319] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted, in addition to deionized water, ofphosphonic compounds, with a very high level of compound based on1,12-dodecanediphosphonic acid.

[0320] In this case, drying produced a dry film of on average less than80 nm in thickness, in particular of one or a few molecular layers, thephosphonic compounds orienting themselves predominantly perpendicular tothe surface. After cooling to room temperature, a second, inventivetreatment was then carried out with a second bath solution in accordancewith Table 11, as described in example 30.

Inventive Example 40

[0321] Alloy-galvanized or hot galvanized steel sheets, as described inexample 30, were treated with the treatment liquid specified below,dried, and tested. The bath solution consisted of

[0322] 2 g/l hexafluorozirconic acid,

[0323] 0.3 g/l Al(OH)₃,

[0324] 1.8 g/l polyacrylic acid (molecular weight: about 100 000),

[0325] 2 g/l SiO₂ (as colloidal silica dispersion), and

[0326] 1 g/l MnCO₃.

[0327] After cooling to room temperature, a second, inventive treatmentwas then carried out with the second bath solution in accordance withTable 11, as described in example 30.

[0328] In the case of example 41 and of the comparative examples 11 to13 only the first treatment was carried out.

Inventive Example 41

[0329] Alloy-galvanized or hot galvanized steel sheets, as described inexample 30, were treated with the treatment liquid corresponding toTable 11, dried, and tested.

Comparative Example 10

[0330] Steel sheets which, starting from commercial cold-rolled steelstrip, were alloy-galvanized by coating with 55% AlZn (Galvalume®) orhot dip galvanized by immersion in zinc melt (HDG), and which thereafterwere oiled for the purpose of protection during storage, and cut, werefirst of all degreased in an alkaline spray cleaner, rinsed with water,dried at elevated temperature, and then treated with a first aqueouscomposition. A defined amount of the aqueous composition (bath solution)was applied by means of a rollcoater so as to give a wet film thicknessof 10 ml/m². At temperatures in the range from 80 to 100° C. PMT the wetfilm was subsequently dried, filmed, and cured. The bath solution had acomposition in accordance with Table 11.

Comparative Example 11

[0331] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted essentially of a mixture of 67% byweight 1,2-bis(triethoxysilyl)ethane and 33% by weightaminopropyltriethoxysilane, to which acetic acid (glacial acetic acid),technical-grade denatured methanol, and demineralized water were added.The silane content of the solution used was 1.6% by weight. The aceticacid served here to adapt the pH, the methanol content to facilitate thehydrolysis of the silanes. The dry film thickness was set by way of theconcentration of the solution. In this case, drying produced a dry filmof about 160 nm in thickness.

Comparative Example 12

[0332] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin example 30, were treated with the treatment liquid below, dried, andtested. The bath solution consisted, in addition to deionized water, ofphosphonic compounds, with a very high level of compound based on1,12-dodecanediphosphonic acid. In this case, drying produced a dry filmof on average less than 80 nm in thickness, in particular of one or afew molecular layers, the phosphonic compounds orienting themselvespredominantly perpendicular to the surface.

Comparative Example 13

[0333] Alloy-galvanized or hot-dip-galvanized steel sheets, as describedin comparative example 10, were treated with the treatment liquidspecified below, dried, and tested. The bath solution consisted of

[0334] 2 g/l hexafluorozirconic acid,

[0335] 0.3 g/l Al(OH)₃,

[0336] 1.8 g/l polyacrylic acid (molecular weight: about 100 000),

[0337] 2 g/l SiO₂ (as colloidal silica dispersion), and

[0338] 1 g/l MnCO₃.

[0339] Results of the Tests on Galvalume® Sheets and onHot-Dip-Galvanized (HDG) Sheets

[0340] The dry layer add-on of the dried, filmed, cured, and also, whereappropriate, thermally cured, polymer-containing coatings is apparentapproximately from Table 11. All coatings according to the inventionwere transparent and colorless and exhibited a slight silky gloss, sothat the optical character of the metallic surface remained visible withno alteration. TABLE 12 Results of the corrosion control tests onGalvalume ® in salt spray test ASTM B 117-73 Areal Areal Areal ArealAreal corrosion corrosion corrosion corrosion corrosion after 24 h after48 h after 120 h after after in % in % in % 240 h in % 480 h in % I 30 00 0 0 2 I 31 0 0 0 0 0 I 32 0 0 0 0 0 I 33 0 0 0 0 0 I 34 0 0 0 0 0 I 350 0 0 0 0 I 36 0 0 0 0 2 I 37 0 0 0 0 0 I 38 0 0 0 0 0 I 39 0 0 0 0 0 I40 0 0 0 0 0 C 10 2 5 10 15 20 I 41 0 0 2 2 5 C 11 5 5 10 10 15 C 12 1030 50 100 not applicable C13 10 30 50 100 not applicable

[0341] TABLE 13 Results of the corrosion control tests onhot-dip-galvanized steel of grade Z 250 in salt spray test ASTM B 117-73Areal Areal Areal Areal Areal corrosion corrosion corrosion corrosioncorrosion after 24 h after 48 h after 120 h after after in % in % in %240 h in % 480 h in % I 30 0 0 5 15 30 I 31 0 0 2 10 20 I 32 0 0 2 10 20I 33 0 0 2 10 20 I 34 0 0 2 10 20 I 35 0 0 20 10 20 I 36 0 0 5 15 30 I37 0 0 5 15 30 I 38 0 0 50 10 20 I 39 0 0 10 20 30 I 40 0 0 10 20 30 C10 50 100 not not not applicable applicable applicable I 41 0 2 5 10 40C 11 5 5 10 20 50 C 12 50 100 not not not applicable applicableapplicable C13 50 100 not not not applicable applicable applicable

[0342] TABLE 14 Results of the corrosion control tests constantcondensation climate test to DIN 50 017 CC and stacking test onGalvalume ® Constant Constant condensation condensation climate testclimate test Stacking Stacking DIN 50 017 CC DIN 50 017 CC test arealtest edge areal areal corrosion corrosion corrosion corrosion afterafter 28 after 28 after 960 h in % 1920 h in % days in % days in mm I 300 10 0 <1 I 31 0 0 0 <1 I 32 0 0 0 <1 I 33 0 0 0 <1 I 34 0 0 0 <1 I 35 00 0 <1 I 36 0 10 0 <1 I 37 0 5 0 <1 I 38 0 0 0 <1 I 39 0 0 0 <1 I 40 0 00 <1 C 10 10 40 100 completely corroded I 41 0 5 0   2 C 11 10 30 100completely corroded C 12 30 40 100 completely corroded C 13 30 40 100completely corroded

[0343] TABLE 15 Results of the corrosion control tests constantcondensation climate test to DIN 50 017 CC and stacking test on HDGConstant Constant condensation condensation climate test climate testStacking Stacking DIN 50 017 CC DIN 50 017 CC test areal test edge arealareal corrosion corrosion corrosion corrosion after after 28 after 28after 960 h in % 1920 h in % days in % days in mm I 30 0 10 <5   3 I 310 0 <2 <1 I 32 0 0 <2 <1 I 33 0 0 <2 <1 I 34 0 0 <2 <1 I 35 0 0 <2 <1 I36 0 10 <2 <1 I 37 0 5 <2 <1 I 38 0 0 <2 <1 I 39 0 0 <2 <1 I 40 0 0 <2<1 C 10 10 40 100 completely corroded I 41 0 10 <5   2 C 11 10 30 100completely corroded C 12 30 40 100 completely corroded C 13 30 40 100completely corroded

[0344] The smallest values in the corrosion tests of Tables 12 and 15show the best results. In comparison to examples 30 to 40, comparativeexamples 10 to 13 show much poorer, and example 41 slightly poorer,corrosion control values of the single-layer surface treatment incomparison to the two-layer surface treatment.

[0345] The stacking test was performed as described previously.

[0346] The mechanical tests on Galvalume® sheets and, respectively, inthe case of HDG took place in a test chamber to DIN 50 017 CC for a testperiod of 4 weeks. An assessment is then made as to what kind of rust(red rust, black rust, white rust) has developed in the edge region andwhat percentage area is affected by the rust. An assessment is also madeas to what kind of rust has developed over the entire surface area andof how great the percentage corroded area fraction on the treated sheetsurface is. Galvalume® sheets in this test exhibit first white or blackcorrosion and, like steel, if the aluminum-zinc alloy coating has beenconsumed or has been damaged right through to the steel sheet, exhibitred corrosion. The results were identical for both types of substrate.TABLE 16 Results of the mechanical tests, tested on Galvalume ® sheetsand HDG respectively: Mandrel bending test with conical mandrel fromKönig pendulum 3.2 mm to 38 mm hardness to DIN in diameter, to Erichsen53 157 DIN ISO 6860 cupping test I 30 60 no cracks unaffected I 31 60 nocracks unaffected I 32 60 no cracks unaffected I 33 60 no cracksunaffected I 34 60 no cracks unaffected I 35 60 no cracks unaffected I36 60 no cracks unaffected I 37 60 no cracks unaffected I 38 60 nocracks unaffected I 39 60 no cracks unaffected I 40 60 no cracksunaffected C 10 not applicable cracks cracked, abrasion I 41 60 nocracks unaffected C 11 not applicable cracks cracked, abrasion C 12 notapplicable cracks cracked, abrasion C 13 not applicable cracks cracked,abrasion

[0347] The pendulum hardness was averaged over 5 measurements in eachcase, the values being rounded up or down accordingly. The lower thependulum hardness, the softer the film and also, usually, the better theadhesion of the film to the metallic surface.

[0348] The ductile properties of the coating of the invention were setso that the coating is neither too soft nor too hard for the mechanicalattack of the tools during forming. As a result, a substantiallyundamaged coating remains after the forming operation. Moreover, as aresult of these ductile properties, the cut edges are relatively wellprotected, since the coating does not fragment at the cut edges and insome cases is even drawn up at the cut edge, so that increased edgeprotection is achieved.

[0349] The mandrel bending test is evidence of the good flexibility andgood adhesion of the coating to the metallic substrate, and of itsoutstanding formability.

[0350] Forming took place as described previously with a cup-drawingmachine from Erichsen, model 142-20, with a sheet holder force of 2500kp and with a drawing force of 2 Mp. From the Galvalume® sheet sectionstreated in accordance with the invention, disks of 60 mm in diameterwere punched, and were drawn to hat-shaped cups with a brim generallyabout 15 to 17 mm in depth and with a cup diameter of about 35 mm. Thegood forming properties therefore appear to derive from the presence oforganic substance, especially oxidized polyethylene, and are positivelyinfluenced by the presence of inorganic particles.

[0351] It is anticipated that the experiments performed on Galvalume®sheets and hot-dip-galvanized sheets and the results determined can betransferred to sheets provided with AlSi, ZnAl, ZnFe, ZnNi, Al, and Zncoatings without changing the process parameters and lead to virtuallyidentical results.

1. A method of coating a metallic strip, the strip, or where appropriatestrip sections produced from it, in the subsequent operation being firstcoated with at least one anticorrosion layer and then with at least onelayer of a paintlike, polymer-containing layer, the strip, after coatingwith at least one anticorrosion layer or after coating with at least onelayer of a paintlike coating, being divided into strip sections, thecoated strip sections then being formed, joined and/or coated with atleast one (further) paintlike layer and/or paint layer, the paintlikecoating being formed by coating the surface with an aqueous dispersionwhich comprises besides water a) at least one organic film formercomprising at least one water-soluble or water-dispersed polymer havingan acid number in the range from 5 to 200, b) at least one inorganiccompound in particle form, having an average particle diameter, measuredin a scanning electron microscope, in the range from 0.005 up to 0.3 μmdiameter, and c) at least one lubricant and/or at least one corrosioninhibitor, the metallic surface coated with at least one anticorrosionlayer being contacted with the aqueous composition and aparticle-containing film being formed on the metallic surface, andsubsequently dried and, as the case may be, additionally cured, thedried and, as the case may be, additionally cured film having athickness in the range from 0.01 to 10 μm.
 2. A method of coating ametallic strip, the strip being coated with at least one layer of apaint-like, polymer-containing layer without an anti-corrosion layerbeing applied beforehand, the strip, after coating with at least onelayer of a paintlike coating, being divided into strip sections, thecoated strip sections then being formed, joined and/or coated with atleast one (further) paintlike layer and/or paint layer, the paintlikecoating being formed by coating the surface with an aqueous dispersionwhich comprises besides water a) at least one organic film formercomprising at least one water-soluble or water-dispersed polymer havingan acid number in the range from 5 to 200, b) at least one inorganiccompound in particle form, having an average particle diameter, measuredin a scanning electron microscope, in the range from 0.005 up to 0.3 μmdiameter, and c) at least one lubricant and/or at least one corrosioninhibitor, the clean metallic surface being contacted with the aqueouscomposition and a particle-containing film being formed on the metallicsurface, and subsequently dried and, as the case may be, additionallycured, the dried and, as the case may be, additionally cured film havinga thickness in the range from 0.01 to 10 μm.
 3. The method of claim 1 or2, characterized in that a surface of aluminum, iron, copper, magnesium,nickel, titanium, tin, zinc or alloys of aluminum, iron, copper,magnesium, nickel, titanium, tin and/or zinc is coated.
 4. The method ofany of the, above claims, characterized in that aqueous composition issubstantially or entirely free from chromium(VI) compounds.
 5. Themethod of any of the above claims, characterized in that the element tobe coated—in particular a strip or strip section—is subjected to formingafter having been coated.
 6. The method of any of the above claims,characterized in that aqueous composition comprises at least one organicsolvent, one silane and/or siloxane calculated as silane, at least onecrosslinking agent, especially one based on a basic compound, and/or atleast one chromium(VI) compound.
 7. The method of any of the aboveclaims, characterized in that the organic film former is in the form ofa solution, dispersion, emulsion, microemulsion and/or suspension. 8.The method of any of the above claims, characterized in that organicfilm former is at least one synthetic resin, in particular a syntheticresin based on acrylate, ethylene, polyester, polyurethane, siliconepolyester, epoxide, phenol, styrene, urea-formaldehyde, derivativesthereof, copolymers, polymers, mixtures and/or addition copolymers. 9.The method of any of the above claims, characterized in that the organicfilm former is a synthetic resin mixture and/or addition copolymer whichincludes synthetic resin based on acrylate, epoxide, ethylene,urea-formaldehyde, phenol, polyester, polyurethane, styrene and/orstyrene-butadiene, and from which, during or after the emission of waterand other volatile constituents, an organic film is formed.
 10. Themethod of any of the above claims, characterized in that the organicfilm former comprises synthetic resins and/or polymers and/orderivatives, copolymers, polymers, mixtures and/or addition copolymersbased on acrylate, epoxide, phenol, polyethyleneimine, polyurethane,polyvinyl alcohol, polyvinylphenol, polyvinylpyrrolidone and/orpolyaspartic acid, especially copolymers with a phosphorus-containingvinyl compound.
 11. The method of any of the above claims, characterizedin that the molecular weights of the synthetic resins, copolymers,polymers and/or derivatives thereof, mixtures and/or addition copolymersare in the region of at least 1000 u, preferably of at least 5000 u,with particular preference from 20 000 to 200 000 u.
 12. The method ofany of the above claims, characterized in that the pH of the organicfilm former in an aqueous formulation, without the addition of furthercompounds, is in the range from 1 to
 12. 13. The method of any of theabove claims, characterized in that the organic film former containsonly water-soluble synthetic resins and/or polymers, especially thosewhich are stable in solutions with pH values ≦5.
 14. The method of anyof the above claims, characterized in that the organic film formercontains synthetic resin and/or polymer which contain carboxyl groups.15. The method of any of the above claims, characterized in that theacid groups of the synthetic resins have been stabilized with ammonia,with amines such as morpholine, dimethylethanolamine,diethylethanolamine or triethanolamine, for example, and/or with alkalimetal compounds such as sodium hydroxide, for example.
 16. The method ofany of the above claims, characterized in that the aqueous compositioncontains from 0.1 to 1000 g/L of the organic film former, preferablyfrom 2 to 600 g/L.
 17. The method of any of the above claims,characterized in that the aqueous composition comprises at least onepartly hydrolyzed or completely hydrolyzed silane.
 18. The method of anyof the above claims, characterized in that at least one aminosilane,epoxysilane, vinylsilane and/or at least one corresponding siloxane ispresent.
 19. The method of any of the above claims, characterized inthat the amount of at least one silane and/or siloxane, calculated assilane, in the aqueous composition is preferably from 0.1 to 50 g/L. 20.The method of any of the above claims, characterized in that asinorganic compound in particle form a finely divided powder, adispersion or a suspension such as, for example, a carbonate, oxide,silicate or sulfate is added, especially colloidal and/or amorphousparticles.
 21. The method of any of the above claims, characterized inthat as inorganic compound in particle form particles having an averagesize in the range from 8 nm to 150 nm are used.
 22. The method of any ofthe above claims, characterized in that as inorganic compound inparticle form particles based on at least one compound of aluminum,barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zincand/or zirconium are added.
 23. The method of any of the above claims,characterized in that as inorganic compound in particle form particlesbased on alumina, barium sulfate, cerium dioxide, silica, silicate,titanium oxide, yttrium oxide, zinc oxide and/or zirconium oxide areadded.
 24. The method of any of the above claims, characterized in thatthe aqueous composition comprises from 0.1 to 500 g/L of the at leastone inorganic compound in particle form.
 25. The method of any of theabove claims, characterized in that the aqueous composition comprises atleast one corrosion inhibitor, based in particular on amine(s),preferably at least one alkanolamine, at least one conductive polymerand/or at least one thiol.
 26. The method of any of the above claims,characterized in that the aqueous composition comprises at least onecrosslinking agent based on a basic compound, preferably at least onebased on titanium, hafnium and/or zirconium and/or based on carbonate orammonium carbonate.
 27. The method of any of the above claims,characterized in that the aqueous composition is free from inorganicacids and/or organic carboxylic acids.
 28. The method of any of theabove claims, characterized in that as organic solvent for the organicpolymers at least one water-miscible and/or water-soluble alcohol, oneglycol ether or N-methylpyrrolidone and/or water is used, in the case ofthe use of a solvent mixture in particular a mixture of at least onelong-chain alcohol, such as propylene glycol, for example, an esteralcohol, a glycol ether and/or butanediol with water, but preferablyjust water without organic solvent.
 29. The method of any of the aboveclaims, characterized in that the amount of organic solvent is from 0.1to 10% by weight.
 30. The method of any of the above claims,characterized in that as lubricant at least one wax selected from thegroup consisting of paraffins, polyethylenes, and polypropylenes isused, in particular an oxidized wax.
 31. The method of claim 30,characterized in that the melting point of the wax used as lubricant isin the range from 40 to 160° C.
 32. The method of any of the aboveclaims, characterized in that additionally a conductive polymer isadded.
 33. The method of any of the above claims, characterized in thatadditionally at least one photoinitiator is added in order to allowcuring by exposure to actinic radiation.
 34. The method of claim 33,characterized in that the coating is cured partly by actinic radiationand partly by drying and filming or thermal crosslinking.
 35. The methodof any of the above claims, characterized in that the aqueouscomposition comprises where appropriate in each case at least onebiocide, defoamer and/or wetting agent.
 36. The method of any of theabove claims, characterized in that an aqueous composition having a pHin the range from 0.5 to 12 is used.
 37. The method of any of the aboveclaims, characterized in that the aqueous composition is applied with atemperature in the range from 5 to 50° C. to the metallic surface. 38.The method of any of the above claims, characterized in that themetallic surface is held at temperatures in the range from 5 to 120° C.on application of the coating.
 39. The method of any of the aboveclaims, characterized in that the coated metallic surface is dried at atemperature in the range from 20 to 400° C. PMT (peak metaltemperature).
 40. The method of any of the above claims, characterizedin that the coated strips are wound to a coil, where appropriate aftercooling to a temperature in the range from 40 to 70° C.
 41. The methodof any of the above claims, characterized in that the aqueouscomposition is applied by rolling, flowcoating, knifecoating, spraying,squirting, brushing or dipping and, where appropriate, by subsequentsqueezing off with a roll.
 42. The method of any of the above claims,characterized in that the dried and also, where appropriate, cured filmhas a pendulum hardness of from 30 to 190 s, measured with a Königpendulum hardness tester in accordance with DIN
 53157. 43. The method ofany of the above claims, characterized in that the dried and also, whereappropriate, cured film has a flexibility such that bending over aconical mandrel in a mandrel bending test very substantially inaccordance with DIN ISO 6860 for a mandrel of from 3.2 mm to 38 mm indiameter—but without scoring of the test area—produces no cracks longerthan 2 mm which are perceptible when subsequently wetted with coppersulfate as a result of color change as a consequence of copperdeposition on the cracked metallic surface.
 44. The method of any of theabove claims, characterized in that in each case at least one coatingcomprising varnish, polymers, paint, adhesives and/or adhesive backingis applied to the dried and also, where appropriate, cured film.
 45. Themethod of any of the above claims, characterized in that the coatedmetal parts, especially strips or strip sections are formed, painted,coated with polymers such as PVC, for example, printed, bonded,hot-soldered, welded and/or joined to one another or to other elementsby clinching or other joining techniques.
 46. The method of any of theabove claims, characterized in that the strip or the strip sectionsis/are cut, where appropriate, after painting with a paintlike coatingand the painted strip sections during cutting and/or then are formed andthereafter joined, where appropriate, to other shaped parts, inparticular by crimping, clinching, adhesive bonding, welding and/oranother mechanical joining technique.
 47. The method of any of the aboveclaims, characterized in that at least two or three anticorrosion layersare applied in succession, of which each of these two or three layers isan anticorrosion layer selected from the group consisting of coatingsbased in each case on iron-cobalt, nickel-cobalt, at least one fluoride,at least one complex fluoride, especially tetrafluoride and/orhexafluoride, an organic hydroxy compound, a phosphate, a phosphonate, apolymer, a rare earth compound, including lanthanum and yttriumcompounds, a silane/siloxane, a silicate, cations of aluminum, magnesiumand/or at least one transition metal selected from the group consistingof chromium, iron, hafnium, cobalt, manganese, molybdenum, nickel,titanium, tungsten, and zirconium, or is a coating based onnanoparticles, but it is also possible where appropriate for at leastone further anticorrosion layer to be applied.
 48. The method of any ofthe above claims, characterized in that the first anticorrosion layer isapplied in a drying method and in that the second anticorrosion layer isapplied in a drying method or rinse method.
 49. The method of any of theabove claims, characterized in that the first anticorrosion layer isapplied by a rinse method and in that the second anticorrosion layer isapplied by a drying method or rinse method.
 50. The method of any of theabove claims, characterized in that the second anticorrosion layer isapplied in an afterrinsing step, in particular after the firstanticorrosion layer has been applied beforehand on a galvanizing line.51. The method of any of the above claims, characterized in that thesecond anticorrosion layer is applied in a drying method, in particularafter the first anticorrosion layer has been applied beforehand on agalvanizing line.
 52. The method of any of the above claims,characterized in that surfaces of aluminum, iron, cobalt, copper,magnesium, nickel, titanium, tin or zinc or alloys comprising aluminum,iron, cobalt, copper, magnesium, nickel, titanium, tin and/or zinc,especially electrolytically galvanized or hot-dip-galvanized surfacesare coated.
 53. The method of any of the above claims, characterized inthat coating is carried out with at least one liquid, solution orsuspension which is substantially or entirely free from chromiumcompounds before coating with at least one paint and/or with at leastone paintlike polymer-containing layer which comprises polymers,copolymers, crosspolymers, oligomers, phosphonates, silanes and/orsiloxanes.
 54. The method of any of the above claims, characterized inthat no lead, cadmium, chromium, cobalt, copper and/or nickel is addedto the liquid, solution or suspension for the first and/or secondanticorrosion layer.
 55. The method of any of the above claims,characterized in that because of the at least one anticorrosion layer—ascompared with the state of the art on the priority date—it is possibleto forego at least one of the otherwise customary pretreatment layers,paint layers and/or paintlike polymer-containing layers, in particular apretreatment layer and a paint layer.
 56. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers and/or paintlikepolymer-containing layers comprises, in addition to water, at least oneorganic film former with at least one water-soluble or water-dispersedpolymer, copolymer, block copolymer, crosspolymer, monomer, oligomer,derivative(s) thereof, mixture thereof and/or addition copolymerthereof.
 57. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers and/or paintlike polymer-containing layers[lacuna], in addition to water, a total content of cations, tetrafluorocomplexes and/or hexafluoro complexes of cations selected from the groupconsisting of titanium, zirconium, hafnium, silicon, aluminum, and boronand/or free or otherwise-bound fluorine, in particular from 0.1 to 15g/L complex fluoride based on F₆, preferably from 0.5 to 8 g/L complexfluoride based on F₆, or from 0.1 to 1000 mg/L of free fluorine.
 58. Themethod of any of the above claims, characterized in that the liquid,solution and/or suspension for at least one of the anticorrosion layersand/or paintlike polymer-containing layers [lacuna], in addition towater, a total content of free fluorine or fluorine not attached totetrafluoro or hexafluoro complexes, in particular from 0.1 to 1000 mg/Lcalculated as free fluorine, preferably from 0.5 to 200 mg/L, morepreferably from 1 to 150 mg/L.
 59. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises, in addition to water, at least oneinorganic compound in particle form having an average particle diameter,measured under a scanning electron microscope, in the range from 0.003up to 1 μm diameter, preferably in the range from 0.005 up to 0.2 μmdiameter, based in particular on Al₂O₃, BaSO₄, rare earth oxide(s), atleast one other rare earth compound, SiO₂, silicate, TiO₂, Y₂O₃, Zn, ZnOand/or ZrO₂, preferably in an amount in the range from 0.1 to 80 g/L,more preferably in an amount in the range from 1 to 50 g/L, verypreferably in an amount in the range from 2 to 30 g/L.
 60. The method ofany of the above claims, characterized in that the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layers orpaintlike polymer-containing layers [lacuna] at least one corrosioninhibitor selected from the group consisting of organic phosphatecompounds, phosphonate compounds, organic morpholine and thio compounds,aluminates, manganates, titanates, and zirconates, preferably ofalkylmorpholine complexes, organic Al, Mn, Ti and/or Zr compoundsespecially of the olefinically unsaturated carboxylic acids, forexample, ammonium salt of carboxylic acids such as chelated lactic acidtitanate, triethanolamine titanate or triethanolamine zirconate,Zr-4-methyl-γ-oxo-benzyne-butanoic acid, aluminum zirconium carboxylate,alkoxypropenolatotitanate or alkoxypropenolatozirconate, titaniumacetate and/or zirconium acetate and/or derivatives thereof, Ti/Zrammonium carbonate.
 61. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers or paintlikepolymer-containing layers comprises at least one compound for theneutralization, in particular the slow neutralization, of comparativelyacidic mixtures and/or for the corrosion control of unprotected ordamaged portions of the metallic surface, based preferably on carbonateor hydroxycarbonate or conductive polymers, more preferably at least onebasic compound with a layer structure such as, for example,Al-containing hydroxy-carbonate hydrate (hydrotalcite).
 62. The methodof any of the above claims, characterized in that the liquid, solutionor suspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers in addition to watercomprises at least one silane and/or siloxane, calculated as silane, inparticular in an amount in the range from 0.1 to 50 g/L, preferably inan amount in the range from 1 to 30 g/L.
 63. The method of any of theabove claims, characterized in that the liquid, solution or suspensionfor at least one of the anticorrosion layers, paint layers and/orpaintlike polymer-containing layers in addition to water and/or at leastone organic solvent comprises at least one silane and/or siloxane,calculated as silane, in particular in an amount in the range from 51 to1300 g/L.
 64. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers where appropriate in addition to water and/or at least oneorganic solvent comprises at least one silane and/or siloxane,calculated as silane, in particular in an amount in the range from 0.1to 1600 g/L, preferably in an amount in the range from 100 to 1500 g/L.65. The method of any of the above claims, characterized in that theliquid, solution or suspension for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layerscomprises an organic film former in the form of a solution, dispersion,emulsion, microemulsion and/or suspension.
 66. The method of any of theabove claims, characterized in that the liquid, solution or suspensionfor at least one of the anticorrosion layers, paint layers and/orpaintlike polymer-containing layers comprises as organic film former atleast one synthetic resin, in particular at least one synthetic resinbased on acrylate, ethylene, polyester, polyurethane,silicone-polyester, epoxide, phenol, styrene, styrene-butadiene,urea-formaldehyde, their derivatives, copolymers, block copolymers,crosspolymers, monomers, oligomers, polymers, mixtures and/or additioncopolymers.
 67. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises as organic film former a synthetic resin mixture and/oraddition copolymer comprising synthetic resin based on acrylate,ethylene, urea-formaldehyde, polyester, polyurethane, styrene and/orstyrene-butadiene and/or their derivatives, copolymers, crosspolymers,oligomers, polymers, mixtures and/or addition copolymers, from which anorganic film is formed during or after the emission of water and othervolatile constituents.
 68. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises as organic film former syntheticresins and/or polymers, copolymers, block copolymers, crosspolymers,monomers, oligomers, polymers, mixtures and/or addition copolymersand/or their derivatives based on acrylate, polyethyleneimine,polyurethane, polyvinyl alcohol, polyvinylphenol, polyvinyl-pyrrolidoneand/or polyaspartic acid, especially copolymers with aphosphorus-containing vinyl compound.
 69. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises a synthetic resin whose acid numberis in the range from 5 to
 250. 70. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises synthetic resins and/or polymers,copolymers, block copolymers, crosspolymers, monomers, oligomers,polymers, mixtures and/or addition copolymers and/or derivatives thereofwhose molecular weights are in the range of at least 1000 u, preferablyof at least 5000 u or of up to 500 000 u, more preferably in the rangefrom 20 000 to 200 000 u.
 71. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises synthetic resins and/or polymers,copolymers, block copolymers, crosspolymers, monomers, oligomers,polymers, mixtures and/or addition copolymers and/or derivativesthereof, in particular based inter alia on pyrrolidone(s), in particularfrom 0.1 to 500 g/L, preferably from 0.5 to 30 or from 80 to 250 g/L.72. The method of any of the above claims, characterized in that theliquid, solution or suspension for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layerscomprises an organic film former whose pH in an aqueous formulationwithout addition of further compounds is in the range from 1 to
 12. 73.The method of any of the above claims, characterized in that the liquid,solution or suspension for at least one of the anticorrosion layers,paint layers and/or paintlike polymer-containing layers comprises anorganic film former which contains only water-soluble synthetic resinsand/or polymers, copolymers, block copolymers, crosspolymers, monomers,oligomers, polymers, mixtures and/or addition copolymers and/or theirderivatives, particularly those which are stable in solutions with pHlevels ≦5.
 74. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises an organic film former whose synthetic resin and/orpolymers, copolymers, block copolymers, crosspolymers, monomers,oligomers, polymers, mixtures and/or addition copolymers and/or theirderivatives contain carboxyl groups.
 75. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises an organic film former in which theacid groups of the synthetic resins and/or polymers, copolymers, blockcopolymers, crosspolymers, monomers, oligomers, polymers, mixturesand/or addition copolymers and/or their derivatives have been stabilizedwith ammonia, with amines such as morpholine, dimethylethanolamine,diethylethanolamine or triethanolamine, for example, and/or with alkalimetal compounds such as sodium hydroxide, for example.
 76. The method ofany of the above claims, characterized in that the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprises from 0.1 to 200 g/Land preferably from 0.3 to 50 g/L of the organic film former.
 77. Themethod of any of the above claims, characterized in that the liquid,solution or suspension for at least one of the anticorrosion layers,paint layers and/or paintlike polymer-containing layers comprises from100 to 2000 g/L and preferably from 300 to 1800 g/L of the organic filmformer.
 78. The method of any of the above claims, characterized in thatthe liquid, solution or suspension for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers includea monomer fraction, in particular in the region of at least 5% byweight, preferably of at least 20% by weight, more preferably of atleast 40% by weight.
 79. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises from 0.1 to 50 g/L of cations,tetrafluoro complexes and/or hexafluoro complexes of cations selectedfrom the group consisting of titanium, zirconium, hafnium, silicon,aluminum, and boron.
 80. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises at least one organometalliccompound, particularly containing titanium and/or zirconium.
 81. Themethod of any of the above claims, characterized in that the liquid,solution or suspension for at least one of the anticorrosion layers,paint layers and/or paintlike polymer-containing layers includes atleast one silane and/or siloxane calculated as silane in the aqueouscomposition, preferably in a range from 0.2 to 40 g/L, more preferablyin a range from 0.5 to 10 g/L.
 82. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises at least one partly hydrolyzedsilane, at least one wholly hydrolyzed silane and/or at least onesiloxane.
 83. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises at least one partly hydrolyzed and/or nonhydrolyzedsilane, in particular in the case of a silane content of more than 100g/L, more preferably in the case of a silane content of more than 1000g/L.
 84. The method of any of the above claims, characterized in thatthe liquid, solution or suspension for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layerscomprises in each case at least one acyloxysilane, alkylsilane,aminosilane, bis-silyl-silane, epoxysilane, fluoroalkylsilane,glycidyloxysilane, isocyanatosilane, mercaptosilane,(meth)acrylatosilane, mono-silyl-silane, multi-silyl-silane,sulfur-containing silane, ureidosilane, vinylsilane and/or at least onecorresponding siloxane.
 85. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers has added to it as inorganic compound inparticle form a finely divided powder, a dispersion or a suspension suchas, for example, a carbonate, oxide, silicate or sulfate, especiallycolloidal or amorphous particles.
 86. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers has added to it as inorganic compound inparticle form particles having an average size in the range from 4 nm to150 nm, in particular in the range from 10 to 120 nm.
 87. The method ofany of the above claims, characterized in that the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers has added to it as inorganiccompound in particle form particles based on at least one compound ofaluminum, barium, cerium, calcium, lanthanum, silicon, titanium,yttrium, zinc and/or zirconium.
 88. The method of any of the aboveclaims, characterized in that to the liquid, solution or suspension forat least one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises from 0.1 to 300 g/L of the at leastone inorganic compound in particle form.
 89. The method of any of theabove claims, characterized in that the liquid, solution or suspensionis used for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers as organic solvent for theorganic polymers at least one water-miscible and/or water-solublealcohol, one glycol ether and/or one pyrrolidone such as, for example,N-methylpyrrolidone and/or water; where a solvent mixture is used, it isin particular a mixture of at least one long-chain alcohol, such aspropylene glycol, for example, an ester alcohol, a glycol ether and/orbutanediol with water, but preferably only water without organicsolvent.
 90. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises organic solvent in an amount in the range from 0.1 to10% by weight.
 91. The method of any of the above claims, characterizedin that the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises as lubricant at least one wax selected from the groupconsisting of paraffins, polyethylenes, and polypropylenes, inparticular an oxidized wax.
 92. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises a wax lubricant whose melting pointis in the range from 40 to 160° C., preferably from 0.1 to 100 g/L, morepreferably from 20 to 40 g/L or from 0.1 to 10 g/L, very preferably 0.4to 6 g/L, for example, a crystalline polyethylene wax.
 93. The method ofany of the above claims, characterized in that the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprises at least one rareearth element compound, in particular at least one compound selectedfrom the group consisting of chloride, nitrate, sulfate, sulfamate, andcomplexes, for example, with a halogen or with an aminocarboxylic acid,in particular complexes with EDTA, NTA or HEDTA, in which contextscandium, yttrium, and lanthanum are also regarded as being rare earthelements.
 94. The method of any of the above claims, characterized inthat the liquid, solution or suspension for at least one of theanticorrosion layers, paint layers and/or paintlike polymer-containinglayers comprises a rare earth element compound of and/or with cerium, inparticular in a mixture with other rare earth elements, for example, atleast partly based on mixed metal.
 95. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises at least one oxidizing agent, inparticular a peroxide, at least one accelerator and/or at least onecatalyst, preferably a compound and/or ions of Bi, Cu and/or Zn.
 96. Themethod of any of the above claims, characterized in that the liquid,solution or suspension for at least one of the anticorrosion layers,paint layers and/or paintlike polymer-containing layers comprises atleast one compound selected from the group of the mono-, bis-, andmulti-silanes, especially: mono-silanes of the general formulaSiX_(m)Y_(4-m) with m=1 to 3, preferably m=2 to 3, with X=alkoxy,especially methoxy, ethoxy and/or propoxy, and with Y as a functionalorganic group selected from the group consisting of acyloxy, alkyl,acrylate, amino, epoxy, fluoroalkyl, glycidyloxy, urea, isocyanate,mercapto, methacrylate and/or vinyl and/or derivatives thereof,bis-silanes of the general formula Y_(3-p)X_(p)—Si-Z-Si—X_(n)Y_(3-n)with p and n=1 to 3, identical or different, with X=alkoxy, especiallymethoxy, ethoxy and/or propoxy, and with Y as a functional organic groupselected from the group consisting of acyloxy, alkyl, acrylate, amino,epoxy, fluoroalkyl, glycidyloxy, urea, isocyanate, mercapto,methacrylate and/or vinyl and/or derivatives thereof, with Z selectedfrom the group of C_(n)H_(2n) with n=2 to 20, in each case branched orunbranched, of singly unsaturated alkyl chains of the general formulaC_(n)H_(2n-2) with n=2 to 20, in each case branched or unbranched, ofdoubly and/or multiply unsaturated alkyl compounds of the generalformulae C_(n)H_(2n-4) with n=4 to 20, in each case branched orunbranched, C_(n)H_(2n-6) with n=6 to 20, in each case branched orunbranched, or C_(n)H_(2n-8) with n=8 to 20, in each case branched orunbranched, of ketones, monoalkylamines, NH, and sulfur S_(q) with q=1to 20, multi-silanes of the general formulaY_(3-p)X_(p)—Si-Z′-Si—X_(n)Y_(3-n) with p and n=1 to 3, identical ordifferent, with X=alkoxy, especially methoxy, ethoxy and/or propoxy, andwith Y as a functional organic group selected from the group consistingof acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl, glycidyloxy,urea, isocyanate, mercapto, methacrylate, mono/bis/multi-silyl and vinyland/or derivatives thereof, and with Z′=N—Si—X_(r)Y_(3-r) with r=1 to 3or sulfur S_(q) with q=1 to 20, multi-silanes of the general formulaY_(3-p)X_(p)—Si-Z″-Si—X_(n)Y_(3-n) with p and n=1 to 3, identical ordifferent, with X=alkoxy, especially methoxy, ethoxy and/or propoxy, andwith Y as a functional organic group selected from the group consistingof acyloxy, alkyl, acrylate, amino, epoxy, fluoroalkyl, glycidyloxy,urea, isocyanate, mercapto, methacrylate, mono/bis/multi-silyl and vinyland/or derivatives thereof, and withZ″=—R—C[(SiX_(s)Y_(3-s))(SiX_(t)Y_(3-t))]—R′— or sulfur S_(q) with q=1to 20, with s and t=1 to 3, identical or different, with R and R′,identical or different, selected from the group of C_(n)H_(2n) with n=2to 20, in each case branched or unbranched, of singly unsaturated alkylchains of the general formula C_(n)H_(2n-2) with n=2 to 20, in each casebranched or unbranched, of doubly and/or multiply unsaturated alkylcompounds of the general formulae C_(n)H_(2n-4) with n=4 to 20, in eachcase branched or unbranched, C_(n)H_(2n-6) with n=6 to 20, in each casebranched or unbranched, or C_(n)H_(2n-8) with n=8 to 20, in each casebranched or unbranched, of ketones, monoalkylamines, NH, it beingpossible for the silanes in each case to be present in hydrolyzed,partly hydrolyzed and/or nonhydrolyzed form in a solution, emulsionand/or suspension.
 97. The method of any of the above claims,characterized in that the liquid, solution or suspension for at leastone of the anticorrosion layers comprises at least one compound of thetype XYZ, X*Y*Z* and/or X*Y*Z*Y*X*, where Y is an organic group having 2to 50 carbon atoms where X and Z, identical or different, are an OH, SH,NH₂, NHR′, CN, CH═CH₂, OCN, CONHOH, COOR′, acrylamide, epoxide,CH₂═CR″—COO, COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH)(OR′)PO,(OH)(OR′)PO₂, SiH₃ and/or an Si (OH)₃ group, where R′ is an alkyl grouphaving 1 to 4 carbon atoms, where R″ is a hydrogen atom or an alkylgroup having 1 to 4 carbon atoms, where the groups X and Z are eachattached to the group Y in the terminal position thereof, where Y* is anorganic group having 1 to 30 carbon atoms, where X* and Z*, identical ordifferent, are an OH, SH, NH₂, NHR′, CN, CH═CH₂, OCN, CONHOH, COOR′,acrylamide, epoxide, CH₂═CR″—COO, COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂,(OH)(OR′)PO, (OH)(OR′)PO₂, SiH₃, Si(OH)₃, >N—CH₂—PO(OH)₂ and/or an—N—[CH₂—PO(OH)₂]₂ group, where R′ is an alkyl group having 1 to 4 carbonatoms, and where R″ is a hydrogen atom or an alkyl group having 1 to 4carbon atoms.
 98. The method of any of the above claims, characterizedin that the liquid, solution or suspension for at least one of theanticorrosion layers comprises at least one compound of the type XYZ,where X is a COOH, HSO₃, HSO₄, (OH)₂PO, (OH)₂PO₂, (OH)(OR′)PO or(OH)(OR′)PO₂ group, where Y is an organic group R containing 2 to 50carbon atoms, of which at least 60% of these carbon atoms are present inthe form of CH₂ groups, where Z is an OH, SH, NH₂, NHR′, CN, CH═CH₂,OCN, epoxy, CH═CR″—COOH, acrylamide, COOH, (OH)₂PO, (OH)₂PO₂,(OH)(OR′)PO or (OH)(OR′)PO₂ group, where R′ is an alkyl group having 1to 4 carbon atoms, and where R″ is a hydrogen atom or an alkyl grouphaving 1 to 4 carbon atoms, preferably in total from 0.01 to 10 g/L,preferably from 0.05 to 5 g/L, very preferably from 0.08 to 2 g/L. 99.The method of any of the above claims, characterized in that thecompound of type XYZ, X*Y*Z* and/or X*Y*Z*Y*X* is suitable for formingself-arranging molecules, which may shape a layer of theseself-arranging molecules particularly on the metallic surface,preferably a monomolecular layer.
 100. The method of any of the aboveclaims, characterized in that the liquid, solution or suspension for atleast one of the anticorrosion layers comprises at least one of thefollowing compounds of type XYZ, X*Y*Z* and/or X*Y*Z*Y*X*: 1-phosphonicacid-12-mercaptododecane, 1-phosphonic acid-12-(N-ethylaminododecane),1-phosphonic acid-12-dodecene, p-xylylenediphosphonic acid,1,10-decanediphosphonic acid, 1,12-dodecanediphosphonic acid,1,14-tetradecanediphosphonic acid, 1-phosphoric acid-12-hydroxydodecane,1-phosphoric acid-12-(N-ethylamino)dodecane, 1-phosphoricacid-12-dodecene, 1-phosphoric acid-12-mercaptododecane,1,10-decanediphosphoric acid, 1,12-dodecanephosphoric acid,1,14-tetradecanediphosphoric acid, p,p′-biphenyldiphosphoric acid,1-phosphoric acid-12-acryloyldodecane, 1,8-octanediphosphonic acid,1,6-hexanediphosphonic acid, 1,4-butanediphosphonic acid,1,8-octanediphosphoric acid, 1,6-hexanediphosphoric acid,1,4-butanediphosphoric acid, aminotrimethylenephosphonic acid,ethylenediaminetetramethylenephosphonic acid,hexamethylenediaminetetramethylenephosphonic acid,diethylenetriaminepentamethylenephosphonic acid,2-phosphonobutane-1,2,4-tricarboxylic acid.
 101. The method of any ofthe above claims, characterized in that at least one of the liquids,solutions or suspensions for at least one of the anticorrosion layersand/or paintlike polymer-containing layers comprises phosphate and zinc,where appropriate also manganese, nickel and/or copper.
 102. The methodof any of the above claims, characterized in that at least one of theliquids, solutions or, suspensions for at least one of the anticorrosionlayers and/or paintlike polymer-containing layers contains from 0.2 toless than 50 g/L of zinc ions, from 0.5 to 45 g/L manganese ions, andfrom 2 to 300 g/L phosphate ions, calculated as P₂O₅.
 103. The method ofany of the above claims, characterized in that at least one of theliquids, solutions or suspensions for at least one of the anticorrosionlayers and/or paintlike polymer-containing layers comprises phosphate,preferably based on Zn or ZnMn, where appropriate with nickel content.104. The method of any of the above claims, characterized in that atleast one of the liquids, solutions or suspensions for at least one ofthe anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises phosphate, fluoride, tetrafluorideand/or hexa-fluoride.
 105. The method of any of the above claims,characterized in that at least one of the liquids, solutions orsuspensions for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers may comprise phosphonate,tetrafluoride and/or hexafluoride.
 106. The method of any of the aboveclaims, characterized in that at least one of the liquids, solutions orsuspensions for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprises an organic filmformer, fluoride, tetrafluoride, hexafluoride and/or at least oneinorganic compound in particle form, and, where appropriate, at leastone silane.
 107. The method of any of the above claims, characterized inthat at least one of the liquids, solutions or suspensions for at leastone of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers comprises an additive selected from the groupconsisting of organic binders, biocides, defoamers, corrosioninhibitors, adhesion promoters, wetting agents, photoinitiators, andpolymerization inhibitors.
 108. The method of any of the above claims,characterized in that at least one of the liquids, solutions orsuspensions for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprises at least one fillerand/or one pigment, in particular at least one electrically conductivepigment selected from the group consisting of dyes, color pigments,graphite, graphite-mica pigments, oxides such as iron oxides,phosphates, phosphides such as iron phosphides, carbon black and zinc.109. The method of any of the above claims, characterized in that priorto the application of an anticorrosion layer, paint layer and/orpaintlike polymer-containing layer, an activating treatment is applied.110. The method of any of the above claims, characterized in that theapplication of an anticorrosion layer, paint layer or paintlikepolymer-containing layer may be followed by application of an afterrinseand/or passivation.
 111. The method of any of the above claims,characterized in that at least one of the liquids, solutions orsuspensions for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers comprises an organic filmformer which, following application to the metallic substrate, is curedby heat and/or actinic radiation, in particular by electrons, UV and/orradiation in the visible light region.
 112. The method of any of theabove claims, characterized in that at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers may beonly partly cured prior to adhesive bonding, welding, and/or forming andnot fully cured until after adhesive bonding, welding and/or forming,the first curing before adhesive bonding, welding and/or forming takingplace by actinic radiation—in particular by electrons, UW and/orradiation in the visible light region—and the second curing taking placeafter adhesive bonding, welding and/or forming, preferably thermally, inparticular by radiant heat and/or hot air.
 113. The method of any of theabove claims, characterized in that the liquid, solution or suspensionfor at least one of the anticorrosion layers, paint layers and/orpaintlike polymer-containing layers has a pH in the range from 0.5 to12.
 114. The method of any of the above claims, characterized in thatthe liquid, solution or suspension for at least one of the anticorrosionlayers, paint layers and/or paintlike polymer-containing layers isapplied to the respective surface at a temperature in the range from 5to 95° C., preferably in the range from 5 to 50° C.
 115. The method ofany of the above claims, characterized in that the substrate and/or therespective surface are held during application of the anticorrosionlayer(s) at temperatures in the range from 5 to 120° C.
 116. The methodof any of the above claims, characterized in that the coated metallicsurface in this case is dried at a temperature in the range from 20 to400° C. PMT (peak metal temperature).
 117. The method of any of theabove claims, characterized in that the coated strips are cut up orwound to a coil, where appropriate after cooling to a temperature in therange from 10 to 70° C.
 118. The method of any of the above claims,characterized in that the divided strips, after pressing, cutting and/orpunching, are coated in the edge region with a temporarily appliedcoating to be removed again or with a permanently protecting coating,e.g., at least one coating based on dry lubricant, phosphate,hexafluoride, paintlike coating and/or paint.
 119. The method of any ofthe above claims, characterized in that the liquid, solution orsuspension for at least one of the anticorrosion layers, paint layersand/or paintlike polymer-containing layers is applied by rolling,flowcoating, knifecoating, spraying, squirting, brushing or dipping and,where appropriate, by subsequent squeezing off with a roll.
 120. Themethod of any of the above claims, characterized in that the coatingapplied in each case with the liquid, solution or suspension for atleast one of the anticorrosion layers, paint layers and/or paintlikepolymer-containing layers is adjusted to a layer weight in the rangefrom 0.0005 mg/m² to 150 g/m², preferably in the range from 0.0008 mg/m²to 30 g/m², more preferably in the range from 0.001 mg/m² to 10 g/m², inparticular in the range from 1 to 6 g/m².
 121. The method of any of theabove claims, characterized in that to the partly or fully cured filmthere is applied in each case at least one coating of paint or of apaintlike, polymer-containing coating to the partly or fully cured film,the first paint layer or paintlike polymer-containing layer may consistessentially of primer, a thinly (i.e., in the range from 0.1 to 10 μm)applied, organic-polymer-containing material, a reaction primer, a shopprimer or a wash primer.
 122. The method of any of the above claims,characterized in that at least one coating of paint, a mixture of orwith polymers, varnish, adhesive and/or adhesive backing to the at leastpartly painted strip or the strip at least partly coated in a paintlikemanner with a polymer-containing layer, or to the at least partlypainted strip section or the strip section coated at least partly in apaintlike manner with a polymer-containing layer is applied.
 123. Themethod of any of the above claims, characterized in that the clean orcleaned and, where appropriate, activated metallic surface is contactedwith the liquid, solution or suspension for one of the anticorrosionlayers and at least one film, which where appropriate may also containparticles, may be formed on the metallic surface, which is subsequentlydried and, where appropriate, additionally cured, the dried and, whereappropriate, also cured film possibly having in each case a thickness inthe range from 0.01 to 100 μm, in particular a film with a thickness inthe range from 5 up to 50 μm, more preferably in the range from 8 up to30 μm.
 124. The method of any of the above claims, characterized in thatat least one paint layer as undercoat or one paintlikepolymer-containing layer as pretreatment primer, primer, primer asreplacement of the cathodic dip coat, lubricating primer, reactionprimer, welding primer, wash primer, clearcoat and/or topcoat, whereappropriate instead of an undercoat is applied.
 125. The method of anyof the above claims, characterized in that at least one of the paintlayers and/or paintlike polymer-containing layers is cured by heatand/or actinic radiation, in particular by UV radiation.
 126. The methodof any of the above claims, characterized in that the coated strips orstrip sections are formed, painted, coated with polymers such as PVC,for example, printed, bonded, hot soldered, welded and/or joined withone another or with other elements by clinching or other joiningtechniques.
 127. An aqueous composition for pretreating a metallicsurface prior to a further coating or for treating that surface,characterized in that the composition comprises in addition to water a)at least one organic film former which comprises at least onewater-soluble or water-dispersed polymer having an acid number in therange from 5 to 200, b) at least one inorganic compound in particle formhaving an average particle diameter, measured under a scanning electronmicroscope, in the range from 0.005 up to 0.3 μm diameter, c) at leastone lubricant and/or at least one corrosion inhibitor, d) if desired, atleast one organic solvent, e) if desired, at least one silane and/orsiloxane, calculated as silane, f) if desired, at least one crosslinkingagent, especially based on a basic compound, and g) if desired, at leastone chromium(VI) compound.
 128. Use of the substrates coated by themethod of at least one of the above claims 1 to 126, such as, forexample, a wire, a strip or a part, characterized in that the substrateto be coated is wire winding, wire mesh, steel strip, metal sheet,paneling, shield, vehicle body or part of a vehicle body, part of avehicle, trailer, recreational vehicle or missile, cover, casing, lamp,light, traffic light element, furniture item or furniture element, anelement of a household appliance, frame, profile, molding of complexgeometry, guideboard element, radiator element or fencing element,bumper, part of or with at least one pipe and/or profile, window frame,door frame or cycle frame, or a small part such as, for example, a bolt,nut, flange, spring or a spectacle frame.
 129. The use of the productsproduced by the method of at least one of claims 1 to 126 in vehicleconstruction, in particular in automotive production-line manufacture,for producing components or bodywork parts or premounted elements in thevehicle, air travel or space travel industry; as metal sheet, paneling,bodywork or part of a bodywork, as part of a vehicle, trailer,recreational vehicle or missile, as a cover, profile, shaped part ofcomplex geometry, bumper, part of or with at least one pipe and/orprofile.